JP2019066829A - Radiation sensitive resin composition and application thereof - Google Patents

Abstract

To provide a radiation sensitive resin composition capable of achieving both of radiation sensitivity and so called PCD, PED margin property.SOLUTION: There is provided a radiation sensitive resin composition containing a polymer component (A) having a structural unit (I) containing an aromatic ring and an alkoxysilyl group directly bound to the aromatic ring and a structural unit (II) containing an acidic group excluding a structural unit derived from aromatic unsaturated carboxylic acid and a hydroxy fluoride alkyl group-containing monomer in same or different polymer, a radiation sensitive compound (B) and an organic solvent (G).SELECTED DRAWING: None

Description

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

  Generally, a cured film such as an interlayer insulating film, a spacer, a protective film, and a patterned colored film (also referred to as a “colored pattern film” in the present specification) for a color filter is used for a semiconductor element. 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 this specification) is small, and high surface hardness can be obtained. Resin compositions are widely used.

  As a radiation sensitive resin composition, the radiation sensitive resin composition containing the copolymer containing a carboxy group and an epoxy group is known, for example (refer patent document 1). There is also known a positive photosensitive composition containing a polymer obtained by radical copolymerization of a radically polymerizable monomer having an alkoxysilyl group and a radically polymerizable monomer having an acidic group (see Patent Document 2). .

JP 2001-354822 A JP, 2013-101240, A

  In conventional radiation sensitive resin compositions, it has been difficult to achieve both radiation sensitivity and so-called post coating delay (PCD) and post exposure delay (PED) margin characteristics. For example, the PED margin is the width of the delay time from the irradiation to the development treatment, and the composition preferably has high radiation sensitivity even when the PED margin is large.

  An object of the present invention is to provide a radiation sensitive resin composition, a pattern film and a method for producing the same, a semiconductor element, and a display device, which can realize the above-mentioned coexistence.

  The present inventors diligently studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by a radiation sensitive resin composition having the following constitution, and the present invention has been completed.

The present invention relates to, for example, the following [1] to [13].
[1] Structural unit (I) containing an aromatic ring and an alkoxysilyl group directly bonded to the aromatic ring in the same or different polymer, and structural unit (II) containing an acidic group (with the exception of aromatic groups Characterized by containing a polymer component (A) having a structural unit derived from a saturated carboxylic acid and a hydroxy-fluorinated alkyl group-containing monomer), a radiation sensitive compound (B), and an organic solvent (G) Radiation sensitive resin composition to be.
[2] The radiation sensitive resin composition according to [1], wherein the radiation sensitive compound (B) contains at least one compound selected from a radiation sensitive acid generator and a radiation sensitive base generator.
[3] The radiation sensitive resin composition of the above [1] or [2] which further contains at least one compound (C) selected from a thermal acid generator and a thermal base generator.
[4] The radiation sensitive resin composition according to any one of the above [1] to [3], which further contains a cohesion aid.
[5] The radiation sensitive resin composition according to any one of the above [1] to [4], which further contains an acid diffusion control agent.
[6] The radiation sensitive resin composition according to any one of the above [1] to [5], which further contains a solubility promoter.
[7] The polymer component (A) is crosslinkable in the same or different polymer as a 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 [6], further having a structural unit (III) containing a group.
[8] A group represented by the structural unit (I), which is a substituted or unsubstituted benzene ring, naphthalene ring or anthracene ring, and -SiR ₃ directly bonded to the ring (the R is each independently hydrogen A structural unit containing an atom, a halogen atom, a hydroxy group, an alkyl group, an aryl group, or an alkoxy group; provided that at least one of the R's is an alkoxy group; The radiation sensitive resin composition according to any one of the above.
[9] A patterned cured film formed from the radiation sensitive resin composition of any one of the above [1] to [8].
[10] The patterned cured film of [9], which is an interlayer insulating film.
[11] A step (1) of forming a coating film of the radiation sensitive resin composition according to any one of the above [1] to [8] on a substrate, and a step of irradiating a part of the coating film with radiation. (2) A method for producing a patterned cured film, comprising: (3) developing the coating film irradiated with radiation; and (4) heating the developed coating film.
[12] A semiconductor device comprising the patterned cured film of [9] or [10].
[13] A display device comprising the semiconductor element of the above [12].

  According to the present invention, it is possible to provide a radiation sensitive resin composition capable of achieving both radiation sensitivity and so-called PCD and PED margin characteristics, a pattern film and a method of manufacturing the same, a semiconductor element and a display device.

Hereinafter, modes 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 "the 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 polymer. (I) and a polymer component (A) having a structural unit (II) containing an acidic group (excluding structural units derived from an aromatic unsaturated carboxylic acid and a hydroxy-fluorinated alkyl group-containing monomer); It contains a radioactive compound (B) and an organic solvent (G).

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

<< Structural unit (I) >>
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 a radiation sensitive 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 sensitive characteristics by the structural unit (I). The reason is presumed as follows. Structural unit (I) contains an alkoxysilyl group directly bonded to an aromatic ring. When a coating film of the composition of the present invention is irradiated with radiation, hydrolysis reaction with water in the air or in a developer catalyzed by an acid generated from a radiation sensitive acid generator causes alkoxysilyl groups to silanol groups. (Si-OH) occurs. Since the silanol group is bonded to the aromatic ring, the condensation reaction of the silanol group is inhibited, and the silanol group can be stabilized and present. For this reason, the solubility with respect to the alkali developing solution of a radiation irradiation area | region increases by silanol group. Thus, the composition of the present invention can exhibit positive radiation-sensitive properties. 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 to be formed is unstable, resulting in condensation to the siloxane. For this reason, the radiation irradiated area is insolubilized (negative conversion), and the positive radiation sensitivity characteristic is not exhibited. Moreover, structural unit (I) can improve various characteristics, such as heat resistance of the pattern film obtained, by including an aromatic ring.

  Moreover, when using the radiation sensitive base generator mentioned later as a radiation sensitive compound (B), the composition of this invention can exhibit a highly sensitive negative radiation-sensitive characteristic by Structural-unit (I). . It is presumed that this is because when a coating film of the composition of the present invention is irradiated with radiation, a base generated from the radiation sensitive base generator acts as a catalyst to form a polysiloxane.

The structural unit (I) may be one type of structural unit or plural types of structural units.
The alkoxysilyl group is preferably a group represented by -SiR ₃ . The R's are each 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 aforementioned Rs 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, still more preferably 1.

  Examples of the aromatic ring to which an 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.

  Substituents other than the aforementioned alkoxysilyl group may be bonded to the aromatic ring. As a substituent, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group is mentioned, for example. The number of substituents may be one or two or more, and may be one or more.

Hereinafter, each group in said R and a substituent is demonstrated.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom is mentioned, for example.
As an alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group is mentioned, for example. The carbon number of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3. Methyl is more preferred.

Examples of the aryl group include phenyl group, tolyl group, xylyl group and naphthyl group. The carbon number of the aryl group is preferably 6 to 20, more preferably 6 to 10.
As an alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group is mentioned, for example. The carbon number of the alkoxy group is preferably 1 to 6, more preferably 1 to 3. The methoxy group and the ethoxy group are more preferable, and the methoxy group is more preferable.

As a group which is not an alkoxy group among said R, an alkyl group or a hydroxy group is preferable.
Specific examples of the group represented by -SiR ₃ include trimethoxysilyl group, triethoxysilyl group, tripropoxysilyl group, dimethoxyhydroxysilyl group, dimethoxymethylsilyl group, diethoxyethylsilyl group and methoxydimethylsilyl group. Groups are preferred.
As structural unit (I), the structural unit represented by Formula (1) is mentioned, for example.

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 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 alkoxysilyl group is directly bonded, as described above, 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, for example, a divalent linear hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a divalent divalent hydrocarbon 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 combining the divalent hydrocarbon group and an oxy group (-O-), and a combination of these groups Group is mentioned.

As X, a single bond and -COO- * (* represents a bonding position to 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 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。

Wherein (I-1) ~ (I -20), R A has the same meaning as R ^A in formula (1).

<< Structural unit (II) >>
Structural unit (II) has an acidic group. However, structural units derived from the aromatic unsaturated carboxylic acid and the hydroxy-fluorinated alkyl group-containing monomer are excluded from the structural unit (II). 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 a single structural unit or a plurality of structural units. The structural unit (II) can increase the solubility of the polymer component (A) in a developer and can enhance the curing reactivity.

As an acid dissociation constant of an acidic group, for example, pKa ≦ 12 is preferable, pKa ≦ 10 is more preferable, and pKa ≦ 8 is more preferable. As the acidic group, for example, an amino group, a carboxy group, a sulfo group, a phenolic hydroxyl group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid in which at least one of hydrogen atoms bonded to a nitrogen atom is substituted by an electron withdrawing group. And at least one selected from a group and a sulfonamide group. As an electron withdrawing group, halogen atoms, such as a fluorine atom and a chlorine atom, a nitro group, a cyano group, and a carbonyl group are mentioned, for example. The acidic group is preferably at least one selected from 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, and at least one selected from a maleimide group and a carboxy group More preferable. The acid dissociation constant can be measured as an acid dissociation constant in H ₂ O (water) at 25 ° C. of the acid group in the monomer giving the structural unit (II).

As a hydroxy fluorinated alkyl group, the group represented by Formula (2): -C (R < ² >) (R < ³ >) OH is mentioned. 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 of 1 to 4 carbon atoms or a fluorinated alkyl group of 1 to 4 carbon atoms. Examples of the hydroxyfluorinated alkyl group-containing monomer include 1,1,1,3,3,3-hexafluoro-2- (4-vinylphenyl) -propan-2-ol.

  As the structural unit (II), for example, a structural unit derived from an unsaturated carboxylic acid (excluding structural units derived from an aromatic unsaturated carboxylic acid and a hydroxy-fluorinated alkyl group-containing monomer), a structure derived from maleimide Unit, a structural unit derived from vinyl sulfonic acid.

  Examples of the unsaturated carboxylic acids include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and α-chloroacrylic acid; unsaturated acids such as maleic acid, itaconic acid, citraconic acid, fumaric acid and mesaconic acid Dicarboxylic acids; mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and the like, preferably unsaturated monocarboxylic acids, and the like Preferred is (meth) acrylic acid.

  In the present invention, since the π-π stacking phenomenon occurs in the structural unit (I) and the structural unit (II) and the alkali developability hardly occurs, the unsaturated carboxylic acid is preferably cinnamic acid or phthalic acid monobasic. It is not an aromatic unsaturated carboxylic acid such as [2- (meth) acryloyloxyethyl], 4-vinylbenzoic acid and 4-vinylphenylpropionic acid. The aromatic unsaturated carboxylic acid is an unsaturated carboxylic acid having an aromatic ring.

<< 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 structural units (III) in the same or different polymer as the polymer having structural units (I) and / or (II). The structural unit (III) may be a single structural unit or a plurality of structural units. The structural unit (III) can enhance the curing reactivity and the heat resistance of the obtained patterned film.

  The crosslinkable group is a group other than an alkoxysilyl group and an acidic group, and is, for example, a group capable of reacting with similar groups (for example, epoxy groups) under heating conditions to form a covalent bond. As the crosslinkable group, for example, epoxy group such as oxiranyl group (1,2-epoxy structure), oxetanyl group (1,3-epoxy structure), cyclic carbonate group, methylol group, (meth) acryloyl group, vinyl group It can be mentioned. Among these, oxiranyl group, oxetanyl group and methylol group are preferable, oxiranyl group and oxetanyl group are more preferable, and oxiranyl group is more preferable.

  Examples of the structural unit (III) containing an oxiranyl group include structural units represented by formulas (III-1) to (III-7) and (III-18). Examples of the structural unit (III) containing an oxetanyl group include structural units represented by 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). As structural unit (III) containing a methylol group, the structural unit represented by Formula (III-17) is mentioned, for example.

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), R ^C is a hydrogen atom, a methyl group or a trifluoromethyl group.

  As the structural unit (III) containing a (meth) acryloyl group, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene di (Meth) 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 compounds such as tri (meth) acrylate and pentaerythritol tri (meth) acrylate; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; penta (such as dipentaerythritol penta (meth) acrylate The structural unit derived from monomers, such as a meta) acrylate compound, is mentioned.

  As the structural unit (III) containing a (meth) acryloyl group or a vinyl group, for example, a structural unit obtained by reacting an epoxy group-containing unsaturated compound with a structural unit containing a carboxy group, a structural unit containing an epoxy group Structural units obtained by reacting meta) acrylic acid, structural units obtained by reacting a (meth) acrylic ester or vinyl compound containing an isocyanate group with a structural unit containing a hydroxy group, a structural unit containing an acid anhydride Structural units obtained by reacting (meth) acrylic acid are also mentioned.

<< Structural unit (IV) >>
The polymer component (A) may further have structural units (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 plural types of structural units. By the structural unit (IV), the glass transition temperature of the polymer component (A) can be adjusted to improve the melt flowability at the time of heat curing, and the mechanical strength and chemical resistance of the obtained patterned film.

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

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

Examples of (meth) acrylic acid alicyclic-containing esters include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo (5.2.1.0 ^2,6 ) decane 8-yl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6] decan-8-yl oxy ethyl, and (meth) isobornyl acrylate.

Examples of the (meth) acrylic acid aryl ester include phenyl (meth) acrylate and benzyl (meth) acrylate.
As the N-substituted maleimide compound, for example, N-alkyl group substituted maleimide such as N-methyl maleimide, N-ethyl maleimide, N-tert-butyl maleimide, etc .; N-cycloalkyl group substituted maleimide such as N-cyclohexyl maleimide; And N-aromatic ring-containing group-substituted maleimides such as -phenyl maleimide, N-benzyl maleimide, N- (9-acridinyl) maleimide, N-hydroxyphenyl maleimide and the like.

  Examples of unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate and diethyl itaconate. Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, vinyl toluene, p-methoxystyrene and α-methyl-p-hydroxystyrene. Other unsaturated compounds include, for example, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate, and vinyl acetate. It can be mentioned.

  Among these, as the structural unit (IV), structural units derived from (meth) acrylic acid linear alkyl ester, (meth) acrylic acid alicyclic containing ester, N-substituted maleimide compound, and unsaturated aromatic compound are used. 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, and still more preferably 25% by mass. On the other hand, as this upper limit, 80 mass% is preferred, 60 mass% is more preferred, and 40 mass% is more preferred. In such an embodiment, the composition of the present invention can further improve the heat resistance and the low dielectric property of the obtained patterned film while exhibiting better radiation sensitivity 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, and still more preferably 7% by mass; % By mass is preferable, 40% by mass is more preferable, and 30% by mass is more preferable. In such an embodiment, the composition of the present invention can further improve various properties and the like of the obtained patterned film while exhibiting better radiation-sensitive properties.

  When the polymer component (A) has a structural unit (III), the lower limit of the content ratio of the structural unit (III) to the total structural units in the polymer component (A) is preferably 1% by mass, 3% by mass The upper limit is preferably 75% by mass, more preferably 65% by mass, and still more preferably 55% by mass. In such an embodiment, the composition of the present invention can enhance the radiation sensitivity characteristics and the various characteristics of the obtained patterned 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 the total structural units in the polymer component (A) is preferably 3% by mass, and 5% by mass As the upper limit, 50% by mass is preferable, and 40% by mass is more preferable. Chemical resistance etc. can be effectively improved as it is such a mode.

  The polymer component (A) may be composed of one type of polymer or may be composed of two or more types of polymers, as long as the content of each structural unit measured by NMR analysis satisfies the above requirements, for example. . When it consists of 2 or more types of polymers (blend), the content rate (measurement value) of each structural unit with respect to the whole blend should just satisfy the said requirements.

As the polymer component (A), for example, a copolymer having the structural units (I) and (II), a mixture of a polymer having the structural unit (I) and a polymer having the structural unit (II), a structure A copolymer having units (I), (II) and (III), a mixture of a copolymer having structural units (I) and (II) and a polymer having structural unit (III), a structural unit (I) A mixture of a polymer having a structural unit (II) and a polymer having a structural unit (II) and (III), a polymer having a structural unit (I), a polymer having a structural unit (II) and a structural unit (III) A mixture with a polymer is mentioned. The above-mentioned polymer or copolymer may further have a structural unit (IV).
The term "copolymer having structural units (I) and (II)" means that the same polymer has structural units (I) and (II). The same applies to the other copolymers.

  Furthermore, structural units of the same kind are contained in different polymers, such as a mixture of a copolymer having structural units (I) and (II) and a copolymer having structural units (II) and (III) It may be one. The above-mentioned copolymer may further have a structural unit (IV).

  As the polymer component (A), a copolymer having structural units (I) and (II) is preferable, a copolymer having structural units (I), (II) and (III) is more preferable, and a structural unit Further preferred are copolymers having (I), (II), (III) and (IV).

<< Synthesis Method of Polymer Component (A) >>
The polymer component (A) can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable polymerization solvent using a radical polymerization initiator. In addition, normally, the compounding ratio of each monomer in the case of superposition | polymerization is in agreement with the content rate of a corresponding structural unit in the polymer component (A) obtained. Moreover, as a polymer component (A), several types of polymers are each synthesize | combined, and these plural types of polymers can also be mixed and used after that.

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

As a polymerization solvent, the organic solvent listed as an organic solvent (G) mentioned later is mentioned, for example. The polymerization solvents can be used alone or in combination of two or more.
When the polymerization solvent is the same as the organic solvent (G) in the radiation sensitive resin composition to be prepared, the polymer solution obtained by the above polymerization may be used as it is, or the organic solvent (G) may be added to the obtained polymer solution. You may use for preparation of a radiation sensitive resin composition by adding or.

<< Physical Properties and Content of Polymer Component (A) >>
As for the weight average molecular weight (Mw) of polystyrene conversion by the gel permeation chromatography (GPC) method of a polymer component (A), 1,000-30,000 are preferable. Moreover, as for ratio (Mw / Mn) of Mw of a polymer component (A), and the number average molecular weight (Mn) of polystyrene conversion by GPC method, 1-3 are preferable.

  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; % Is preferable and 97 mass% is more preferable. In such an embodiment, the composition of the present invention can more effectively enhance the radiation sensitivity characteristics and the various characteristics of the obtained patterned film. In addition, total solid content means all components other than an organic solvent (G).

<Radiation sensitive compound (B)>
The radiation sensitive compound (B) (hereinafter also referred to as “component (B)”) is, for example, a radiation sensitive acid generator which is a compound capable of generating an acid by a treatment including radiation, a base comprising a treatment including radiation Radiation-sensitive base generators, which are compounds that generate the acid, and the above-mentioned acid generators are preferable. Examples of radiation include ultraviolet light, far ultraviolet light, visible light, X-rays, and electron beams. As said process, depending on the kind of component (B), only irradiation with radiation may be sufficient, and a water contact process may be required.

  An acid or a base is generated in the irradiated part based on the component (B) by irradiation treatment etc. to the coating film formed from the composition of the present invention, and the alkali of the polymer component (A) based on the action of this acid or base The solubility in the developer changes.

  As a radiation sensitive acid generator, an oxime sulfonate compound, an onium salt, a sulfone imide compound, a halogen containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, a quinone diazide compound is mentioned, for example.

  As specific examples of the oxime sulfonate compound, the onium salt, the sulfone imide compound, the halogen-containing compound, the diazomethane compound, the sulfone compound, the sulfonic acid ester compound and the carboxylic acid ester compound, for example, paragraph [0078] of JP-A 2014-157252 And [0106] and compounds described in WO 2016/124493, and these acid generators are as described herein. Moreover, these acid generators and quinone diazide compounds can also be used in combination.

To illustrate the oxime sulfonate compound, for example, (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene) -(2-Methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) -(2-methylphenyl) acetonitrile, (2- [2- (4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene] -2- (2-methylphenyl) acetonitrile), 2 -(Octyl sulfone Oximino) -2- (4-methoxyphenyl) include acetonitrile.
A specific example is Irgacure PAG121 manufactured by BASF.

  Examples of sulfonimide compounds include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenyl) Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenyl maleimide, N- (camphorsulfonyloxy) Phenylmaleimide, 4-methylphenyl sulfonyloxy) diphenyl maleimide, and trifluoromethanesulfonic acid 1,8-naphthalimide.

  Examples of diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl). Diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) Diazomethane is mentioned.

  As an onium salt, the compound of the following can be mentioned besides the compound of Unexamined-Japanese-Patent No. 2014-157252.

  Examples of quinone diazide compounds include naphthoquinone diazide compounds, which are condensates of compounds having one or more phenolic hydroxyl groups with 1,2-naphthoquinone diazide sulfonic acid halide or 1,2-naphthoquinone diazide sulfonic acid amide. .

  As a specific example of a compound which has one or more phenolic hydroxyl groups, the compound described in stage-of Unexamined-Japanese-Patent No. 2014-186300 is mentioned, for example, These compounds are mentioned in this 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 preferable. As 1,2-naphthoquinonediazide sulfonic acid amide, 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide-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-trile. (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 A compound selected from '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol; And ester compounds with 2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

  As the radiation sensitive base generator, a base generator capable of generating an amine upon irradiation is preferable. Examples of the amine include aliphatic amines and aromatic amines, and may be any of monofunctional amines and polyfunctional amines.

  As a base generator which generates an amine upon irradiation, for example, ortho-nitrobenzyl carbamate compounds, α, α-dimethyl-3,5-dimethoxybenzyl carbamate compounds, other carbamate compounds, acyloxyimino compounds, cobalt amine complexes may be mentioned. Be Specific examples of the base generator that generates an amine upon irradiation with radiation are described, for example, in paragraphs [0104] to [0105] of JP-A-2017-0197378 and paragraph [0045] of JP-A-2017-133006. Compounds, which are intended to be described herein.

  Specific examples of the radiation sensitive base generator include, for example, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, 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-morpholinoethane, (4-morpholinobenzoyl) -1-one Benzyl-1-dimethyla Nopuropan, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - include butanone.

Component (B) can be used alone or in combination of two or more.
The content of the component (B) in the composition of the present invention is usually 0.05 to 30 parts by mass, preferably 0.05 to 20 parts by mass, per 100 parts by mass of the polymer component (A). Preferably, it is 0.05 to 10 parts by mass. The radiation-sensitive acid generator and the base generator can be used in combination, for example, one can be used in a small amount relative to the other. In one embodiment, 10 parts by mass or less of the other of the radiation sensitive acid generator and the base generator can be used with respect to 100 parts by mass.

<Compound (C): Thermal Acid Generator and Thermal Base Generator>
The composition of the present invention can contain at least one compound (C) (hereinafter also referred to as "thermosensitive compound (C)") selected from a thermal acid generator and a thermal base generator. The thermal acid generator is a compound that generates an acid by heat. The thermal base generator is a compound which generates a base by heat. At the time of heating, the dehydration condensation of the residual silanol group in the polymer component (A) is promoted by the acid or the base generated from the above-mentioned generator, and the pattern shape and the chemical resistance of the pattern film are improved.

  It is preferable that the thermal acid generator and the thermal base generator do not generate an acid or a base, or generate only a small amount of an acid or a base, by the heat at the prebaking after the application of the radiation sensitive resin composition.

  Examples of the thermal acid generator include sulfonium salts such as 4-hydroxyphenylbenzylmethylsulfonium bis (trifluoromethanesulfonyl) imide, iodonium salts such as aryliodonium salts, phosphonium salts, quaternary ammonium salts, aluminum chelates, allene- Examples include ion complexes, boron trifluoride amine complexes, and diazomethane compounds.

  As a thermal base generator, for example, carbamate derivatives such as 2- (4-biphenyl) -2-propylcarbamate, 1,1-dimethyl-2-cyanoethylcarbamate and the like; urea, N, N, N'-trimethylurea and the like Urea derivatives; dihydropyridine derivatives such as 1,4-dihydronicotinamide; dicyandiamides; imidazoles such as N- (tert-butoxycarbonyl) -2-phenylimidazole; 1,8-diazabicyclo [5.4.0] undeca-7 Organic salts such as phenol salts of ene, octylate, oleate, p-toluenesulfonate or formate, and octylate of 1,5-diazabicyclo [4.3.0] non-5-ene It can be mentioned. Among these, there are compounds such as N- (tert-butoxycarbonyl) -2-phenylimidazole which can also function as an acid diffusion control agent described later.

  When the compound (C) is used, the content of the compound (C) in the composition of the present invention is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass of the polymer component (A). Is 0.01 to 15 parts by mass, more preferably 0.01 to 10 parts by mass. The thermal acid generator and the thermal base generator can be used in combination, for example, one can be used in a small amount relative to the other. In one embodiment, 10 parts by mass or less of the other can be used with respect to 100 parts by mass of one of the thermal acid generator and the thermal base generator.

<Additives (X), Other Additives (X ')>
The composition of the present invention may further contain at least one additive (X) selected from an adhesion aid, an acid diffusion control agent and a solubility promoter. The composition can further contain at least one other additive (X ′) selected from an antioxidant, a surfactant, a crosslinkable compound, and a polymerization initiator.

  In the composition of the present invention, as the upper limit of the total content ratio of the additives (X) and (X ′) in the total solid content, 20% by mass may be preferable, and 15% by mass is more preferable. 10% by weight may be more preferable.

<< Adhesive aids >>
The composition of the present invention can contain a cohesion aid. The adhesion promoter is a component that improves the adhesion between the pattern film to be obtained and the substrate.

  As a close_contact | adherence adjuvant, a silane coupling agent is mentioned, for example. As a silane coupling agent, a functional silane coupling agent having a reactive functional group such as carboxy group, (meth) acryloyl group, vinyl group, isocyanate group, isocyanurate group, mercapto group, oxiranyl group, oxetanyl group is preferable. . Examples of functional silane coupling agents include carboxy group-containing silane coupling agents such as trimethoxysilylbenzoic acid; polymerizations such as 3- (meth) acryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane and the like Unsaturated double bond-containing silane coupling agent; isocyanate or isocyanurate group-containing silane coupling agent such as 3-isocyanate propyltriethoxysilane and tris- (trimethoxysilylpropyl) isocyanurate; 3-mercaptopropylmethyldimethoxysilane Mercapto group-containing silane coupling agents such as 3-glycidyl oxypropyl trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ethyl-3-oxetanyl methoxy B oxiranyl or oxetanyl group-containing silane coupling agents such as pills trimethoxysilane.

  Among these, oxiranyl group-containing silane coupling agents such as 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, tris- (trimethoxy) An isocyanate or isocyanurate group-containing silane coupling agent such as silylpropyl) isocyanurate, and a mercapto group-containing silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane are obtained by promoting the crosslinking between the polymer components (A) It is preferable from the viewpoint of further improving the chemical resistance of the patterned film.

  The adhesion assistant can be used alone or in combination of two or more. For example, the combined use of an oxiranyl or oxetanyl group-containing silane coupling agent and at least one selected from an isocyanate or isocyanurate group-containing silane coupling agent and a mercapto group-containing silane coupling agent is preferable.

  The content of the adhesion aiding agent in the composition of the present invention in the case of using the adhesion aiding agent is preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polymer component (A), The parts by mass are more preferred.

Acid diffusion control agent
The composition of the present invention can contain an acid diffusion control agent. An acid diffusion control agent controls the diffusion phenomenon in the coating film of the acid which arises from a radiation sensitive acid generator, when the coating film of the composition of this invention is irradiated with radiation, and the undesirable chemical reaction in a non-irradiated part Suppress. By using the acid diffusion control agent, the resolution as the pattern film is improved, and the line width change of the pattern film due to the fluctuation of PED described later can be suppressed, and a composition excellent in process stability can be obtained.

  The acid diffusion control agent is preferably a nitrogen-containing organic compound, and examples thereof include tertiary amine compounds, amide group-containing compounds, quaternary ammonium hydroxide compounds, and nitrogen-containing heterocyclic compounds. Specific examples of these compounds include, for example, compounds described in paragraphs [0205] to [0207] of JP-A-2015-118385, and these compounds are those described in the present specification. Do.

  Specific examples of nitrogen-containing heterocyclic compounds include imidazoles, pyridines and piperazines, and examples of imidazoles include imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl -2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, N- (tert-butoxycarbonyl) -2-phenylimidazole can be mentioned.

An acid diffusion control agent can be used individually or in combination of 2 or more types.
When using an acid diffusion control agent, the content of the acid diffusion control agent in the composition of the present invention is preferably 0.001 to 5 parts by mass, more preferably 100 parts by mass of the polymer component (A). Is 0.001 to 3 parts by mass, more preferably 0.001 to 1 parts by mass.

Solubility accelerator
The composition of the present invention can contain a solubility promoter. As a solubility promoter, a dicarboxylic acid compound is mentioned, for example. As used herein, a dicarboxylic acid compound refers to a compound in which a carbon atom to which one carboxy group is bonded and a carbon atom to which the other carboxy group is bonded are adjacent (that is, bonded). By using a dicarboxylic acid compound, the radiation sensitivity of the resulting composition can be improved.

  Examples of dicarboxylic acid compounds include aliphatic dicarboxylic acids such as succinic acid and fumaric acid; fats such as cyclobutane-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid and cyclohexane-1,2-dicarboxylic acid Mention may be made of dicarboxylic acids having a cyclic structure.

  When using a solubility promoter, the content of the solubility promoter in the composition of the present invention is preferably 1 to 20 parts by mass, more preferably 1 with respect to 100 parts by mass of the polymer component (A). The amount is 15 parts by mass, more preferably 1 to 10 parts by mass.

<Organic solvent (G)>
As an organic solvent (G), each component which the composition of this invention contains is melt | dissolved or disperse | distributed uniformly, and the organic solvent which does not react with said each component is used.
Examples of the organic solvent (G) 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, γ -Ester solvents such as butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, etc. Ether solvents such as ethylene glycol ethyl methyl ether and diethylene glycol methyl ethyl ether N Amide solvents such as N-dimethylacetamide, N-methylpyrrolidone and the like; Chill isobutyl ketone, ketone solvents such as cyclohexanone; toluene, aromatic hydrocarbon solvents such as xylene.

  Among these, as the organic solvent (G), ester solvents, ether solvents and alcohol solvents are preferable. When the organic solvent (G) contains an alcohol solvent, the storage stability of the composition of the present invention can be improved.

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

<Method of Preparing Radiation-Sensitive Resin Composition>
The composition of the present invention is prepared, for example, by mixing the polymer component (A), the component (B), and, if necessary, other components in a predetermined ratio, and dissolving them in an organic solvent (G). The prepared radiation sensitive resin composition is preferably filtered, for example, with a filter having a pore diameter of about 0.2 μm.

<Use of radiation sensitive resin composition>
The composition of the present invention exhibits good radiation-sensitive properties, is excellent in radiation sensitivity, and is excellent in storage stability. By using the composition, it is possible to obtain a patterned film having high resolution and excellent adhesion to a substrate, transparency, and chemical resistance. In particular, the composition has a large post coating delay (PCD) margin and a PED (post exposure delay) margin described in the examples to be described later, and can improve the yield by reducing the defect rate of the pattern film. It is excellent in manufacturing workability.

  Therefore, the composition can be suitably used as a material for forming a cured film for a semiconductor device such as an interlayer insulating film, a spacer, a protective film, and a colored pattern film for color filter, particularly as a material for forming an interlayer insulating film. As said semiconductor element, a display element is mentioned, for example.

[Patterned film]
The patterned film of the present invention is formed from the composition of the present invention. Examples of the pattern film include cured films for semiconductor elements such as interlayer insulating films, spacers, protective films, and colored pattern films for color filters. As the method for producing the pattern film, preferably the following production method is mentioned. The 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.

[Method of manufacturing patterned film]
The method for producing a patterned film of the present invention comprises the steps of: (1) forming a coating of the composition of the present invention on a substrate; (2) irradiating radiation to a part of the coating; And a step (3) of developing the coated film, and a step (4) of heating the developed film.

<Step (1)>
In the step (1), a coating is formed on a substrate using the composition of the present invention. Specifically, the composition in the form of a solution is applied to the substrate surface, and preferably the organic solvent (G) is removed by prebaking to form a coating film.

  Examples of the substrate include a glass substrate, a silicon substrate, a plastic substrate, and a substrate having various metal thin films formed on the surfaces thereof. Examples of the plastic substrate include resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, polycycloolefin and the like. The substrate may be subjected to hydrophobized 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 spin coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method.
The conditions for pre-baking may vary depending on the types, the content ratios, and the like of the respective components, but may be, for example, about 60 seconds to 30 minutes at about 60 seconds to 10 minutes. The film thickness of the coating film to be formed is preferably 0.1 to 10 μm as a value after prebaking.

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

  Moreover, when using a negative radiation sensitive resin composition, heat processing can also be performed after radiation irradiation. Hereinafter, this process is also referred to as "PEB process". PEB conditions differ depending on the type and blending ratio of each component in the radiation sensitive resin composition, the thickness of the resin film, etc., but the temperature is usually 70 to 150 ° C., preferably 80 to 120 ° C., for about 1 to 60 minutes. It is.

<Step (3)>
At the process (3), the said coating film irradiated with the radiation is developed. Specifically, the coating film irradiated with radiation in the step (2) is developed using a developer, and in the case of a positive type, the portion irradiated with radiation is not used, and in the case of a negative type, no radiation is received. Remove the irradiated part. The coating may be wetted with a liquid such as water before development for high sensitivity.

  The developing solution is usually an alkaline developing solution, and examples thereof include an aqueous solution of a basic compound. As the basic compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, 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-nonane. 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 the radiation sensitive resin composition may be used as a developer. .

  Examples of the development method include a liquid deposition method, a dipping method, a rocking immersion 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.

In addition, it is preferable to perform the rinse process by running water washing with respect to the patterned coating film after image development. Further, the radiation sensitive compound (B) remaining in the coating film may be subjected to a decomposition treatment by irradiating (post-exposure) the entire surface with radiation from a high pressure mercury lamp or the like. The amount of exposure in this post-exposure is preferably 2,000 to 5,000 J / m ² .

<Step (4)>
In the step (4), the developed coating is heated. Thus, 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 device, and is, for example, 5 to 40 minutes when heat treatment is performed on a hot plate, and 10 to 80 minutes when 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 element]
The semiconductor device of the present invention is provided with the above-mentioned pattern film, preferably an interlayer insulating film composed of the above-mentioned pattern film. The interlayer insulating film functions as a film that insulates the interconnections in the semiconductor element. The semiconductor device of the present invention can be manufactured using a known method. Since the semiconductor device of the present invention includes the pattern film, it can be suitably used for electronic devices such as display devices, 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, the display device satisfies the general characteristics required in 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. Unless otherwise stated, "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 method.
Measurement method: gel permeation chromatography (GPC) method Equipment: GPC-101 of Showa Denko KK
GPC column: GPC-KF-801, GPC-KF-802, manufactured by Shimadzu LCC
Bond GPC-KF-803 and GPC-KF-804 · Mobile phase: tetrahydrofuran · Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
・ Detector: Differential refractometer ・ Standard substance: Monodispersed polystyrene

[Monomer]
The monomers used in the synthesis of the polymer component are as follows.
<< Monomer giving structural unit (I) >>
· STMS: styryl trimethoxysilane · SDMS: styryl dimethoxyhydroxysilane · STES: styryl triethoxysilane
<< Monomer giving structural unit (II) >>
MA: methacrylic acid AA: acrylic acid HOMS: 2-methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd.)
・ MI: maleimide
<< Monomer giving structural unit (III) >>
OXMA: OXE-30 (Osaka Organic Chemical Industry Co., Ltd.)
(3-ethyl oxetan-3-yl) methyl methacrylate · GMA: glycidyl methacrylate · VBG: p-vinylbenzyl glycidyl ether · ECHMA: 3,4-epoxycyclohexyl methyl methacrylate · EDCPMA: methacrylic acid [3, 4-epoxytrile Cyclo (5.2.1.0 ^2,6 ) decane-9-yl]
<< Monomer giving structural unit (IV) >>
MMA: methyl methacrylate ST: styrene MOI-BM: methacrylic acid 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl (Karen MOI-BM manufactured by Showa Denko KK)
-MPTMS: 3-methacryloxypropyl trimethoxysilane-MPTES: 3-methacryloxypropyl triethoxysilane-VPPA: 4-vinylphenylpropionic acid-HFVP: 1,1,1,3,3,3-hexafluoro-2 -(4-vinylphenyl) propan-2-ol

<Synthesis of Polymer Component (A)>
Synthesis Example 1 Synthesis of Polymer Component (A-1) In a flask equipped with a condenser and a stirrer, 10 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and propylene glycol monomethyl ether acetate 200 I prepared the department. Subsequently, 30 parts of styryltrimethoxysilane, 10 parts of methacrylic acid, 30 parts of glycidyl methacrylate, and 30 parts of methyl methacrylate are charged, and after nitrogen substitution, the temperature of the solution is raised to 70 ° C. while stirring gently. 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 13, Comparative Synthesis Examples 1 to 2
Synthesis of Polymer Components (A-2) to (A-13) and (CA-1) to (CA-2) Synthesis except for using each component of the type and blending amount (parts by mass) shown in Table 1 Polymer components (A-2) to (A-13) and (CA-1) to (CA-2) having a solid content concentration equivalent to that of the polymer component (A-1) in the same manner as in Example 1 ) Was obtained.

<Preparation of radiation sensitive resin composition>
The polymer component (A), the radiation sensitive compound (B), the heat sensitive compound (C), the additive (X) and the organic solvent (G) used for the preparation of the radiation sensitive resin composition are shown below.

<< Polymer component (A) >>
A-1 to A-13: Polymer components synthesized in Synthesis Examples 1 to 13 (A-1) to (A-13)
CA-1 to CA-2: polymer components (CA-1) to (CA-2) synthesized in Comparative Synthesis Examples 1 and 2
Radiation-sensitive compound (B)
B-1: Trifluoromethanesulfonic acid-1, 8-naphthalimide B-2: Irgacure PAG121 (manufactured by BASF Corporation) (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-naphthoquinonediazide-5 Condensation products 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: OS 17 described in WO 2016/124493
B-6: OS 25 described in International Publication No. 2016/124493
B-7: 9-anthrylmethyl N, N-diethyl carbamate
(Wako Pure Chemical Industries, Ltd. WPBG-018)
B-8: 2-hydroxybenzoic acid diphenyl (4- (phenylthio) phenyl) sulfonium
<< Thermosensitive Compound (C) >>
C-1: N- (tert-butoxycarbonyl) -2-phenylimidazole C-2: 4-hydroxyphenylbenzylmethylsulfonium bis (trifluoromethanesulfonyl) imide
<< Additive (X) >>
X-1: 3-glycidyloxypropyltrimethoxysilane X-2: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane X-3: tris- (trimethoxysilylpropyl) isocyanurate
(Shin-Etsu Chemical Co., Ltd.)
X-4: 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
X-5: 3-mercaptopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
X-6: cis-cyclohexanedicarboxylic acid X-7: 4-methyl-2-phenylimidazole
<< organic solvent (G) >>
G-1: Propylene glycol monomethyl ether acetate (PGMEA)
G-2: Diethylene glycol methyl ethyl ether (EDM)
G-3: Propylene glycol monomethyl ether (PGME)
G-4: isoamyl alcohol

<Preparation of radiation sensitive resin composition>
Example 1
The polymer solution containing the polymer (A-1) is mixed with 1 part of the radiation sensitive acid compound (B-1) with respect to an amount corresponding to 100 parts (solid content) of the polymer (A-1) And diluted with an organic solvent (G-1) so that the final solid concentration would be 30% by mass. Next, the resultant was filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation sensitive resin composition.

[Examples 2 to 30, Comparative Examples 1 to 2]
The radiation sensitive resin compositions of Examples 2 to 30 and Comparative Examples 1 to 2 were prepared in the same manner as in Example 1 except that each component of the type and blending amount (parts by mass) shown in Table 2 was used. Prepared. The organic solvent (G) described in Table 2 is an organic solvent type used for dilution.

<Evaluation>
The cured film was formed from the radiation sensitive resin composition of Examples 1-30 and Comparative Examples 1-2, and the following item was evaluated by the method demonstrated below. The evaluation results are shown in Table 2.

Radiation sensitivity
A radiation sensitive resin composition is applied on a HMDS treated silicon substrate 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. It formed. The coating film was irradiated with a predetermined amount of ultraviolet light by a mercury lamp through a pattern mask having a line and space pattern with a width of 10 μm. Next, using a developer consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development was carried out at 25 ° C. for 60 seconds, followed by washing with running ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a 10 μm wide line and space pattern 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 can be evaluated as poor.

[Evaluation of storage stability]
The prepared radiation sensitive resin composition was sealed in a light-tight and airtight container. After 7 days at 25 ° C., the container was opened, 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. If this value is less than 5%, it will be AA; if it is 5% or more and less than 10%, it will be A; if 10% or more and less than 20%, it will be B or 20% or more Was determined to be C. In the case of AA, A or B, the storage stability is good, and in the case of C, the storage stability can be evaluated as poor.

[Evaluation of adhesion to substrate]
A radiation sensitive resin composition is applied on a silicon substrate not subjected to HMDS treatment 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. did. The coating film was irradiated with ultraviolet light with an exposure amount of 400 J / m ² at 365 nm by a mercury lamp through a pattern mask having a line and space pattern with a width of 1 to 50 μm. Next, using a developer consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development was carried out at 25 ° C. for 60 seconds, followed by washing with running ultrapure water for 1 minute. At this time, the minimum width of the line and space pattern remaining without peeling from the substrate was measured. If the measured value is 2 μm or less, AA; if it is more than 2 μm and 5 μm or less, A if it is more than 5 μm and B if 10 μm or less and C if it is more than 10 μm and C or more than 30 μm When it did not reach evaluation, it was judged as D. In the case of AA, A, B or C, the substrate adhesion is good, and in the case of D, the substrate adhesion can be evaluated as being poor.

[Evaluation of PCD Margin and PED Margin]
After applying a radiation sensitive resin composition on a HMDS treated silicon substrate at 60 ° C for 60 seconds using a spinner, (1a) prebaking on a hot plate at 90 ° C for 2 minutes to obtain an average film thickness of 3.0 μm A coating film is formed, and (2a) the coating film is irradiated with a predetermined amount of ultraviolet light by a mercury lamp through a pattern mask having a line and space pattern of 10 μm width, and (3a) coating after ultraviolet irradiation The film was developed for 60 seconds at 25 ° C. using a developer consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and then washed with running ultrapure water for 1 minute. In the case of PCD (Post Coating Delay) margin evaluation, after (1a) and before (2a), and in the case of PED (Post Exposure Delay) margin evaluation, after (2a) and above (3a) The step of leaving the coating at room temperature for 1 hour was added before. At this time, the minimum exposure amount capable of forming a 10 μm wide line and space pattern was measured. This measured value is compared with the measured value of [radiation sensitivity], and the increase rate of the minimum exposure amount is less than 5% as AA, 5% or more and less than 10% is A, and 10% or more and less than 20%. B: A case of 20% or more or a case where the evaluation could not be achieved without resolution was judged as C. In the case of AA, A, and B, the PCD and PED margins can be evaluated as good, and in the case of C, the PCD and PED margins can be evaluated as poor.

[Evaluation of chemical resistance of cured film]
The chemical resistance of the cured film was evaluated as swelling by the peeling liquid. The radiation sensitive resin composition was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating having an average film thickness of 3.0 μm. Then, after irradiating 3000 J / m < ² > light on the whole surface of a substrate using a proximity exposure machine ("MA-1200" (Ghi line mixing) of Canon Inc.), 30 using an oven heated to 230 ° C. It baked for a minute and formed the cured film. This film was immersed in an N-methylpyrrolidone solvent heated to 40 ° C. for 6 minutes, and the film thickness change rate (%) before and after the immersion was determined as an index of chemical resistance. Change rate of film thickness: AA: Change rate of film thickness less than 2%, A: Change rate of film thickness 2% or more and less than 5%, B: Change rate of film thickness 5% or more and less than 10%, C: Change rate of film thickness 10% In the case of AA, A, B or C, the chemical resistance was good, and in the case of D, the chemical resistance was evaluated as poor. The film thickness was measured at 25 ° C. using an optical interference film thickness measuring apparatus (Lambda Ace VM-1010).

  As shown in Table 2, each radiation sensitive resin composition of the example has good radiation sensitivity, and any of storage stability, substrate adhesion, PCD margin, PED margin and chemical resistance as practical characteristics It turns out that it is good. On the other hand, none of the radiation-sensitive resin compositions of the comparative examples had good characteristics.

Claims (13)

Structural unit (I) containing an aromatic ring and an alkoxysilyl group directly bonded to the aromatic ring in the same or different polymer, and structural unit (II) containing an acidic group (however, aromatic unsaturated carboxylic acid And a polymer component (A) having a structural unit derived from a hydroxy-fluorinated alkyl group-containing monomer)
A radiation sensitive compound (B),
A radiation sensitive resin composition comprising an organic solvent (G).   The radiation sensitive resin composition according to claim 1, wherein the radiation sensitive compound (B) contains at least one compound selected from a radiation sensitive acid generator and a radiation sensitive base generator.   The radiation sensitive resin composition according to claim 1 or 2, further comprising at least one compound (C) selected from a thermal acid generator and a thermal base generator.   The radiation sensitive resin composition according to any one of claims 1 to 3, further comprising a cohesion aid.   The radiation sensitive resin composition according to any one of claims 1 to 4, further comprising an acid diffusion control agent.   The radiation sensitive resin composition according to any one of claims 1 to 5, further comprising a solubility promoter.   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 radiation sensitive resin composition according to any one of claims 1 to 6, further comprising a structural unit (III). The structural unit (I) is a substituted or unsubstituted benzene ring, naphthalene ring or anthracene ring, and a group represented by -SiR ₃ directly bonded to the ring (wherein each R is independently a hydrogen atom, halogen 8. A structural unit comprising an atom, a hydroxy group, an alkyl group, an aryl group or an alkoxy group; provided that at least one of the R's is an alkoxy group). Radiation-sensitive resin composition.   The patterned cured film formed from the radiation sensitive resin composition of any one of Claims 1-8.   10. The patterned cured film of claim 9 which is an interlayer dielectric.   The process (1) of forming the coating film of the radiation sensitive resin composition of any one of Claims 1-8 on a board | substrate, the process (2) of irradiating radiation to a part of said coating films, radiation A method for producing a patterned cured film, comprising: a step (3) of developing the above-described coated film which has been irradiated; and a step (4) of heating the developed film.   A semiconductor device comprising the patterned cured film of claim 9 or 10.   A display device comprising the semiconductor device according to claim 12.