JP6528692B2 - Radiation sensitive resin composition, resist pattern forming method, polymer and compound - Google Patents

Description

  The present invention relates to a radiation sensitive resin composition, a method for forming a resist pattern, a polymer and a compound.

  With the miniaturization of various electronic device structures such as semiconductor devices and liquid crystal devices, further miniaturization of the resist pattern in the lithography process is required, and therefore, various radiation sensitive resin compositions are being studied. Such a radiation sensitive resin composition generates an acid in the exposed area by irradiation of exposure light such as far ultraviolet light such as ArF excimer laser, extreme ultraviolet light (EUV), electron beam, etc. A dissolution rate is generated in the developing solution for the portion and the unexposed portion to form a resist pattern on the substrate.

  The radiation sensitive resin composition is not only excellent in resolution and the like but also excellent in LWR (Line Width Roughness) performance, development defect suppression property and rectangularity of the cross-sectional shape of the resist pattern, and also depth of focus and MEEF. (Mask Error Enhancement Factor) It is also required to be excellent in performance and to obtain high precision patterns with high yield. To meet this requirement, various studies have been made on the structure of the polymer contained in the radiation sensitive resin composition, and by having a lactone structure such as a butyrolactone structure or a norbornane lactone structure, adhesion of the resist pattern to the substrate is obtained. It is known that these properties can be improved while enhancing the properties (see JP-A-11-212265, JP-A 2003-5375 and JP-A 2008-83370).

  However, when the miniaturization of resist patterns has progressed to the line width of 45 nm or less, the required level of the above performance is further increased, and the above conventional radiation sensitive resin composition satisfies these requirements. I have not been able to Recently, the shrinkage of the resist film during post-exposure baking (PEB) is required to be small, and as a result, the above-mentioned various resist performances are required to be further improved.

JP-A-11-212265 Unexamined-Japanese-Patent No. 2003-5375 JP 2008-83370 A

  The present invention has been made based on the above circumstances, and the object of the present invention is to provide LWR performance, resolution, rectangularity in cross-sectional shape, depth of focus, MEEF performance, development defect inhibition and film shrinkage inhibition. An object of the present invention is to provide an excellent radiation sensitive resin composition, a method of forming a resist pattern, a polymer and a compound.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子若しくは炭素数１〜２０の１価の有機基であるか、又はこれらの基が互いに合わせられこれらが結合する炭素原子と共に構成される環員数３〜２０の環構造を表す。Ｒ^３は、ヒドロキシ基又は炭素数１〜２０の１価の有機基である。ｎは、０〜１３の整数である。ｎが２以上の場合、複数のＲ^３は同一でも異なっていてもよく、複数のＲ^３のうちの２つが、互いに合わせられ−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−又は−Ｏ−の架橋結合を形成していてもよい。Ｒ^４は、炭素数１〜２０の２価の炭化水素基である。Ｌは、ヘテロ原子を有する２価の連結基である。ｐ及びｑは、それぞれ独立して、１〜３の整数である。＊は、上記構造単位（Ｉ）における上記式（１）で表される基以外の部分に結合する部位を示す。
式（１’）中、Ｅ^１、Ｅ^２及びＥ^３は、それぞれ独立して、酸素原子又は硫黄原子である。Ｒ^３’は、ヒドロキシ基又は炭素数１〜２０の１価の有機基である。ｎ’は、０〜１３の整数である。ｎ’が２以上の場合、複数のＲ^３’は同一でも異なっていてもよく、複数のＲ^３’のうちの２つが、互いに合わせられ−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−又は−Ｏ−の架橋結合を形成していてもよい。Ｒ^４’は、単結合又は炭素数１〜２０の２価の炭化水素基である。Ｌ’は、単結合又はヘテロ原子を有する２価の連結基である。ｐ’及びｑ’は、それぞれ独立して、１〜３の整数である。＊は、上記構造単位（Ｉ）における上記式（１’）で表される基以外の部分に結合する部位を示す。） The invention made to solve the above problems is a first structural unit (hereinafter referred to as “structure”) containing a group represented by the following formula (1) or (1 ′) (hereinafter also referred to as “group (1)”) It contains a polymer (hereinafter also referred to as "[A] polymer") having a unit (I) "and a radiation sensitive acid generator (hereinafter also referred to as" [B] acid generator ") It is a radiation sensitive resin composition.

(In formula (1), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or a carbon in which these groups are combined with each other and these are combined) R ³ represents a ring structure having 3 to 20 ring members, and R ³ is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms, n is an integer of 0 to 13. n is an integer of 0 to 13. In the case of two or more, the plurality of R ^{3 s} may be the same or different, and two of the plurality of R ^{3 s} may be combined with each other to form —CH ₂ —, —CH ₂ —CH ₂ —, —C (CH ₃ ) _And R ⁴ may be a divalent hydrocarbon group having 1 to 20 carbon atoms, and L may be a divalent linking group having a hetero atom. And p and q each independently represent an integer of 1 to 3. * indicates that the structural unit (I) is The site | part couple | bonded with parts other than the group represented by said Formula (1) is shown.
In formula (1 ′), E ¹ , E ² and E ³ are each independently an oxygen atom or a sulfur atom. R ^{3 '} is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. n 'is an integer of 0 to 13. 'If is 2 or more, plural R ^3' n may be the same or different, two of the plurality of R ^{3 ',} are combined with each other _{-CH 2 -, - CH 2 -CH} 2 -, - It may form a C (CH ₃ ) ₂ -or -O- crosslink. R ^{4 ′} is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. L ′ is a single bond or a divalent linking group having a hetero atom. p ′ and q ′ are each independently an integer of 1 to 3. * Shows the site | part couple | bonded with parts other than group represented by said Formula (1 ') in said structural unit (I). )

  Another invention made to solve the above problems comprises a step of forming a resist film, a step of exposing the resist film, and a step of developing the exposed resist film; Pattern forming method using the photosensitive resin composition.

  Another invention made in order to solve the above-mentioned subject is a polymer which has a structural unit containing a group denoted by the above-mentioned formula (1) or (1 ').

  Still another invention made in order to solve the above-mentioned subject is a compound containing a group denoted by the above-mentioned formula (1) or (1 ').

  Here, "organic group" refers to a group containing at least one carbon atom. Moreover, a "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The "hydrocarbon group" may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. "Chain chain hydrocarbon group" refers to a hydrocarbon group that does not contain a cyclic structure and is composed only of a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group. "Alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic structure as a ring structure and not containing an aromatic ring structure, and a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic group Includes both hydrocarbon groups. However, it does not need to be comprised only with an alicyclic structure, and the chain-like structure may be included in the one part. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed of only an aromatic ring structure, and a chain structure or an alicyclic structure may be included in part thereof. "Number of ring members" means the number of atoms constituting the ring of an alicyclic structure, aromatic ring structure, aliphatic heterocyclic structure and aromatic heterocyclic structure, and in the case of a polycyclic ring, the number of atoms constituting this polycyclic ring Say

  According to the radiation sensitive resin composition and resist pattern forming method of the present invention, LWR is small, resolution is high, and rectangular property of cross-sectional shape is excellent while exhibiting excellent depth of focus, MEEF performance and film shrinkage suppressing property. A resist pattern with few development defects can be formed. The polymer of the present invention can be suitably used as a polymer component of the radiation sensitive resin composition. The compound of the present invention can be suitably used as a monomer of the polymer. Therefore, these can be suitably used for semiconductor device manufacture whose miniaturization is expected to further progress in the future.

Radiation-sensitive resin composition
The said radiation sensitive resin composition contains a [A] polymer and a [B] acid generator. The said radiation sensitive resin composition is a [C] acid diffusion control body, [D] [A] polymer other than a fluorine atom containing polymer (Hereinafter, it is also mentioned "[D] polymer") and a suitable component. [E] A solvent may be contained, and other optional components may be contained as long as the effects of the present invention are not impaired. Each component will be described below.

<[A] polymer>
[A] The polymer is a polymer having a structural unit (I). The said radiation sensitive resin composition has LWR performance, resolution, rectangularity of cross-sectional shape, focal depth, MEEF performance, development defect inhibitory property, and a film because [A] polymer has structural unit (I). It is excellent in shrinkage suppression (hereinafter, also referred to as “LWR performance etc.”). It is not necessarily clear about the reason which produces the said effect because the said radiation sensitive resin composition has the said structure, For example, it can guess as follows. That is, when the structural unit (I) of the polymer [A] has a group represented by the above formula (1), -O-CR ¹ R ² -in the ring structure containing -COO- of the formula (1) The acetal structure of O- is bonded, and the ring structure is bonded to a linking group including L containing a hetero atom and a hydrocarbon group R ⁴ . In the above acetal structure, -CR ¹ R ² -is dissociated by the action of an acid generated from an acid generator or the like [B] to generate two hydroxy groups. As a result, since the polarity of the polymer [A] in the exposed area is increased, the dissolution contrast between the exposed area and the unexposed area is improved. Ring structures containing the -COO- has a moderate polarity and bulkiness, and the ring structure via a spacer comprising a L a hydrocarbon radical R ⁴ having the polar [A] polymers Lord It is linked to the chain. As a result, the solubility of the polymer [A] in the developer is adjusted to be more appropriate. [A] The polymer has an appropriately rigid structure due to the bulkiness of the above ring structure and the interaction between the ring structure and the polarity of L. As a result, the diffusion length of the acid generated from the [B] acid generator is adjusted to be more appropriately short. As a result of these, it is considered that the LWR performance and the like of the radiation sensitive resin composition are improved. [A] When the structural unit (I) of the polymer has a group represented by the above formula (1 ′), it is a group having a high polarity in the ring structure containing —COO— of the formula (1 ′) — It has a structure in which E ¹ -C (= E ³ ) -E ² -is bonded. As a result, it is considered that the diffusion to the unexposed area by the acid generated from the [B] acid generator or the like in the exposed area is suppressed, and the MEEF performance and the resolution performance are improved.

  [A] The polymer may be a second structural unit (hereinafter also referred to as “structural unit (II)”) and / or a structural unit (I) other than the structural unit (I), represented by the following formula (2) described later It is preferable to have a third structural unit (hereinafter also referred to as “structural unit (III)”) containing a lactone structure, a cyclic carbonate structure, a sultone structure or a combination thereof, which is a structural unit other than It may have other structural units other than I) to (III). [A] The polymer may have one or more of the above structural units. Each structural unit will be described below.

[Structural unit (I)]
Structural unit (I) is a structural unit containing group (1). The group (1) is a group represented by the following formula (1) or (1 ′).

In the above formula (1), each of R ¹ and R ² independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or a carbon in which these groups are combined with each other It represents a ring structure having 3 to 20 ring members configured together with an atom. R ³ is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 13. When n is 2 or more, plural R ^{3 s} may be the same or different, and two of plural R ^{3 s} may be combined with each other to form —CH ₂ —, —CH ₂ —CH ₂ —, —C (CH 2 ₃ ) A _2- or -O- crosslink may be formed. R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms. L is a divalent linking group having a hetero atom. p and q are each independently an integer of 1 to 3. * Shows the site | part couple | bonded with parts other than group represented by said Formula (1) in said structural unit (I).
Above formula ^{(1 '), E 1,} E 2 and ^{E 3} are each independently an oxygen atom or a sulfur atom. R ^{3 '} is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. n 'is an integer of 0 to 13. 'If is 2 or more, plural R ^3' n may be the same or different, two of the plurality of R ^{3 ',} are combined with each other _{-CH 2 -, - CH 2 -CH} 2 -, - It may form a C (CH ₃ ) ₂ -or -O- crosslink. R ^{4 ′} is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. L ′ is a single bond or a divalent linking group having a hetero atom. p ′ and q ′ are each independently an integer of 1 to 3. * Shows the site | part couple | bonded with parts other than group represented by said Formula (1 ') in said structural unit (I).

The monovalent organic group having 1 to 20 carbon atoms represented by R ¹ and R ² of formula (1), for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, the carbon of the hydrocarbon group - carbon And a group (α) containing a divalent hetero atom-containing group, a group obtained by substituting a part or all of hydrogen atoms of the above hydrocarbon group and group (α) with a monovalent hetero atom-containing group, and the like. .

  As a C1-C20 monovalent hydrocarbon group, a C1-C20 monovalent | monohydric chain hydrocarbon group, a C3-C20 monovalent | monohydric alicyclic hydrocarbon group, C6-C6 is mentioned. 20 monovalent aromatic hydrocarbon groups and the like can be mentioned.

Examples of the monovalent linear hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl and i-propyl;
Alkenyl groups such as ethenyl, propenyl and butenyl;
And alkynyl groups such as ethynyl group, propynyl group and butynyl group.

As a C3-C20 monovalent | monohydric alicyclic hydrocarbon group, monocyclic cycloalkyl groups, such as a cyclopentyl group and a cyclohexyl group, for example;
A monocyclic cycloalkenyl group such as cyclopentenyl group and cyclohexenyl group;
Polycyclic cycloalkyl groups such as norbornyl group, adamantyl group and tricyclodecyl group;
And polycyclic cycloalkenyl groups such as norbornenyl group and tricyclodecenyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group;
And aralkyl groups such as benzyl, phenethyl, naphthylmethyl and anthrylmethyl.

  As a hetero atom which comprises monovalent and divalent hetero atom containing group, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.

  As a bivalent hetero atom containing group, the group etc. which combined 2 or more of these etc. are mentioned, for example, -O-, -CO-, -S-, -CS-, -NR'-. R 'is a hydrogen atom or a monovalent hydrocarbon group. Among these, -O- is preferred.

  As monovalent hetero atom containing group, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a carboxy group, a cyano group, an amino group, sulfanyl group (-SH) etc. are mentioned, for example. Of these, fluorine is preferred.

As a C3-C20 ring structure comprised with these carbon atoms which these groups mutually combine and couple | bond together, a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a cyclooctane structure, for example Etc. monocyclic cycloalkane structure such as
Polycyclic cycloalkane structures such as norbornane structure, adamantane structure, tricyclodecane structure, tetracyclododecane structure;
Single ring arene structure such as indene structure;
Polycyclic arene structures such as fluorene structures;
A single ring oxacycloalkane structure such as oxacyclopentane structure, oxacyclohexane structure;
Examples include polycyclic oxacycloalkane structures such as an oxa norbornane structure and an oxa adamantane structure.

As R ¹ and R ² , a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group and a fluorinated alkyl group are preferable, and a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, a phenyl group and a trifluoromethyl group are more preferable. .

  Examples of the alicyclic structure having 3 to 20 ring members, which are formed together with the carbon atoms to which these groups are combined and the carbon atoms to which they are attached, include a monocyclic cycloalkane structure, a polycyclic cycloalkane structure and a monocyclic oxacycloalkane structure Preferred are cyclohexane structures, adamantane structures and oxacyclopentane structures.

The group represented by, for example ^{-OCOO - - -E 1 -C (=} E 3) -E 2 of the formula (2), - OCOS -, - SCOS -, - OCSO -, - OCOS -, - SCSS -Etc. are mentioned. Among these, -OCOO- and -OCSO- are preferable.

The monovalent organic group having 1 to 20 carbon atoms represented by R ³ and R ^{3 ',} for example, the same groups as those exemplified as the organic group of R ¹ and R ^2, and the like.

As R ³ and R ^{3 ′} , an alkyl group and a hydroxy group are preferable, and a methyl group, an ethyl group and a hydroxy group are more preferable.

Two of the plurality of ^{R 3} or R ^{3 ',} as the cross-linking to form aligned with each _{other, -CH 2 -, - C (} CH 3) 2 - and -O- are preferred.

As n and n ', the integer of 0-4 is preferable, the integer of 0-2 is more preferable, and 0 and 2 are more preferable. When n and n 'are 2, it is preferable that two R ³ or two R ^{3' s} are combined with each other to form a crosslink.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ and R ^{4 ′} include, for example, a divalent linear hydrocarbon group having 1 to 20 carbon atoms and a divalent hydrocarbon group having 3 to 20 carbon atoms. An alicyclic hydrocarbon group, a C6-C20 bivalent aromatic hydrocarbon group, etc. are mentioned.

Examples of the divalent linear hydrocarbon group having 1 to 20 carbon atoms include alkanediyl groups such as methanediyl group, ethanediyl group, propanediyl group and butanediyl group;
Alkenediyl groups such as ethenediyl group, propene diyl group, butene diyl group;
And an alkyndiyl group such as ethynediyl group, propyne diyl group, butindiyl group and the like.

As a C3-C20 bivalent alicyclic hydrocarbon group, monocyclic cycloalkanediyl groups, such as a cyclopentane diyl group and a cyclohexane diyl group, for example;
A monocyclic cycloalkene diyl group such as cyclopentene diyl group and cyclohexene diyl group;
Polycyclic cycloalkanediyl groups such as norbornanediyl group, adamantandiyl group, tricyclodecanediyl group;
Polycyclic cycloalkene diyl groups such as norbornene diyl group and tricyclodecene diyl group can be mentioned.

The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms is, for example, benzenediyl group, toluenediyl group, xylenediyl group, naphthalenediyl group, aurenandiyl group such as anthracenediyl group;
Anarendiylalkanediyl group such as benzenediylmethanediyl group, benzenediylethanediyl group, naphthalenediylmethanediyl group, anthracenediylmethanediyl group and the like can be mentioned.

As R ⁴ , a chain hydrocarbon group and an alicyclic hydrocarbon group are preferable from the viewpoint that the LWR performance and the like of the radiation sensitive resin composition can be further improved, and an alkanediyl group and a cycloalkanediyl group are preferable. An alkanediyl group and a monocyclic cycloalkanediyl group are more preferable, and an alkanediyl group having 1 to 4 carbon atoms and a monocyclic cycloalkanediyl group having 3 to 8 carbon atoms are particularly preferable, and a methanediyl group and an ethanediyl group are more preferable. And cyclohexanediyl group is more particularly preferred, and methanediyl group, 1,1-ethanediyl group, 1,2-ethanediyl group, 1,1-cyclohexanediyl group, 1,2-cyclohexanediyl group and 1,3-cyclohexanediyl group Most preferred.

R ^{4 ′} is preferably a single bond, a chain hydrocarbon group or an alicyclic hydrocarbon group from the viewpoint of being able to further improve the LWR performance and the like of the radiation sensitive resin composition, and a single bond, an alkanediyl Group and cycloalkanediyl group are more preferable, single bond, alkanediyl group and monocyclic cycloalkanediyl group are more preferable, single bond, alkanediyl group having 1 to 4 carbon atoms and single ring having 3 to 8 carbon atoms Particularly preferred is a cycloalkanediyl group, a single bond, a methanediyl group, an ethanediyl group and a cyclohexanediyl group, and a single bond, a methanediyl group, a 1,1-ethanediyl group, a 1,2-ethanediyl group, a 1,1-cyclohexane Diyl, 1,2-cyclohexanediyl and 1,3-cyclohexanediyl are most preferred.

  As a hetero atom which comprises the bivalent coupling group which has a hetero atom represented by L and L ', an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.

  Examples of the divalent linking group having a hetero atom represented by L and L ′ include, for example, -O-, -S-, -NR'-, -CO-, -CS-, or a combination of two or more of them And the like. R 'is a hydrogen atom or a C1-C10 monovalent hydrocarbon group.

  As L, -O-, -COO- and -COCOO- are preferable from the viewpoint of being able to further improve the LWR performance and the like of the radiation sensitive resin composition.

  As L ′, a single bond, —O—, —COO— and —COCOO— are preferable from the viewpoint of being able to further improve the LWR performance etc. of the radiation sensitive resin composition, and a single bond, —O— and -COO- is more preferable, and a single bond is more preferable.

  As p and p ', 1 and 2 are preferable and 1 is more preferable. As q and q ', 1 and 2 are preferable and 2 is more preferable.

Examples of the group (1) include groups represented by the following formulas (a1) to (a32) (hereinafter, “group (
a1) to (a32) "and the like.

  In the above formulas (a1) to (a32), * indicates a site to be bound to a moiety other than the group (1) in the structural unit (I).

  Among these, groups (a1) to (a15), groups (a21), groups (a22), groups (a25), groups (a26), groups (a29) and groups (a30) are preferable.

  As structural unit (I), for example, a structural unit represented by the following formula (1-1) (hereinafter, also referred to as “structural unit (I-1)”), a structure represented by the following formula (1-2) A unit (hereinafter, also referred to as “structural unit (I-2)”), a structural unit represented by the following formula (1-3) (hereinafter, also referred to as “structural unit (I-3)”), and the like can be mentioned.

In the above formulas (1-1) to (1-3), Z is a group represented by the above formula (1) or (1 ').
In the formula (1-1), ^{R 5} is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
In the above formula (1-2), ^{R 6} is a hydrogen atom or a methyl group. R ⁷ is a single bond, -O-, -COO- or -CONH-. R ⁸ is a C 1-10 monovalent organic group. a is an integer of 0 to 4; When a is 2 or more, plural R ^{8 s} may be the same or different.
In the above formula (1-3), ^{R 9} is a hydrogen atom or a methyl group. R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. Two or more of one or more of R ¹⁰ and R ¹¹ and R ¹² may be combined together with the carbon atoms or carbon chains to which they are attached to form a ring structure having 3 to 20 ring members. Good. b is an integer of 1 to 4; When b is 2 or more, plural R ^{10 s} may be the same or different, and plural R ^{11 s} may be the same or different. R ¹³ is a single bond or a divalent organic group having 1 to 20 carbon atoms. R ¹² and R ¹³ may form a ring structure having 3 to 20 ring members, which are configured together with the carbon atoms which are combined with each other and to which they are bonded.

The R ^5, from the viewpoint of copolymerizability of the monomer giving the structural units (I), preferably a hydrogen atom or a methyl group, more preferably a methyl group.
As R ⁶ , a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable, from the viewpoint of the copolymerizability of the monomer giving the structural unit (I).
As R ⁹ , from the viewpoint of the copolymerizability of the monomer giving the structural unit (I), a hydrogen atom and a methyl group are preferable, and a methyl group is more preferable.

As R ⁷ , a single bond, -COO- and -CONH- are preferable, and a single bond is more preferable.

The monovalent organic group having 1 to 10 carbon atoms represented by R ^8, for example, among the groups exemplified as the organic group of R ¹ and R ^2, include such as those having 1 to 10 carbon atoms. Among these, chain hydrocarbon groups and oxy chain hydrocarbon groups are preferable, alkyl groups and alkoxy groups are more preferable, and methyl groups, ethyl groups, methoxy groups and ethoxy groups are more preferable.

  As a, the integer of 0-2 is preferable, 0 and 1 are more preferable, and 0 is more preferable.

As R ¹⁰ , R ¹¹ and R ¹² , a hydrogen atom, a halogen atom and a chain hydrocarbon group having 1 to 10 carbon atoms are preferable, a hydrogen atom, a fluorine atom and an alkyl group are more preferable, and a hydrogen atom, a fluorine atom and methyl Groups are more preferred and hydrogen atoms are particularly preferred.

  As b, the integer of 1-3 is preferable, 1 and 2 are more preferable, and 1 is more preferable.

The ring structure having 3 to 20 ring members, which is formed by combining one or more of R ¹⁰ and R ¹¹ and two or more of R ¹² with each other, is, for example, cyclopropane structure, cyclobutane structure, cyclopentane structure, cyclohexane structure And alicyclic structures such as norbornane structure, adamantane structure and the like; and oxacyclopentane structures, oxacyclohexane structures, azacyclopentane structures, aliphatic heterocyclic structures such as thiacyclopentane structure and the like. The same group etc. are mentioned also as a ring structure of 3-20 ring members comprised by which R < ¹² > and R < ¹³ > are mutually comprised.

Examples of the divalent organic group having 1 to 20 carbon atoms represented by R ^13, for example, group obtained by removing one hydrogen atom from a monovalent organic group exemplified as R ¹ and R ² can be mentioned.

As R ¹³ , a single bond and a divalent hydrocarbon group having 1 to 20 carbon atoms are preferable, a single bond and an alkanediyl group having 1 to 10 carbon atoms are more preferable, and a single bond, a methanediyl group and an ethanediyl group are more preferable. And single bonds are particularly preferred.

  As structural unit (I), structural unit (I-1) is preferable.

  The lower limit of the content ratio of the structural unit (I) is preferably 1 mol%, more preferably 3 mol%, still more preferably 5 mol%, based on all structural units constituting the polymer [A]. % Is particularly preferred. As an upper limit of the content rate of structural unit (I), 80 mol% is preferable, 50 mol% is more preferable, 30 mol% is further more preferable, and 20 mol% is especially preferable. By making the said content rate into the said range, LWR performance etc. of the said radiation sensitive resin composition can be improved more.

  The compound giving the structural unit (I) (hereinafter also referred to as “compound (i)”) contains a group (1).

  As the compound (i), for example, a compound represented by the following formula (i-1) (hereinafter, also referred to as “compound (i-1)”), a compound represented by the following formula (i-2) (hereinafter, Examples thereof include “compound (i-2)”, compounds represented by the following formula (i-3) (hereinafter, also referred to as “compound (i-3)”), and the like.

In the above formulas (i-1) to (i-3), Z is a group represented by the above formula (1) or (1 ').
In the formula (i-1), R ⁵ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
In the formula (i-2), ^{R 6} is a hydrogen atom or a methyl group. R ⁷ is a single bond, -O-, -COO- or -CONH-. R ⁸ is a C 1-10 monovalent organic group. a is an integer of 0 to 4; When a is 2 or more, plural R ^{8 s} may be the same or different.
In the above formula (1-3), ^{R 9} is a hydrogen atom or a methyl group. R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. Two or more of one or more of R ¹⁰ and R ¹¹ and R ¹² may be combined together with the carbon atoms or carbon chains to which they are attached to form a ring structure having 3 to 20 ring members. Good. b is an integer of 1 to 4; When b is 2 or more, plural R ^{10 s} may be the same or different, and plural R ^{11 s} may be the same or different. R ¹³ is a single bond or a divalent organic group having 1 to 20 carbon atoms. R ¹² and R ¹³ may form a ring structure having 3 to 20 ring members, which are configured together with the carbon atoms which are combined with each other and to which they are bonded.

  Examples of the compound (i) include compounds represented by the following formulas (i1) to (i40) (hereinafter, also referred to as “compounds (i1) to (i40)”) and the like.

In the above formulas (i1) to (i40), R ⁵ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ⁶ is a hydrogen atom or a methyl group. R ⁹ is a hydrogen atom or a methyl group.

  Among these, compounds (i1) to (i15), (i25), (i26), (i29), (i30), (i33) and (i34) are preferable.

The compound (i) has, for example, a group represented by the above formula (1), and L is -O-L ^a- (L ^a is ^a divalent group containing ^a hetero atom) and a compound (i-1 In the case of the compound represented by following formula (i'-1) which is), according to the following scheme, it can synthesize | combine simply with sufficient yield.

In the above scheme, R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or these groups are combined with each other together with the carbon atom to which they are attached The ring structure has 3 to 20 ring members. R ³ is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 13. When n is 2 or more, plural R ^{3 s} may be the same or different, and two of plural R ^{3 s} may be combined with each other to form —CH ₂ —, —CH ₂ —CH ₂ —, —C (CH 2 ₃ ) A _2- or -O- crosslink may be formed. R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms. L ^a is a divalent linking group having a hetero atom. p and q are each independently an integer of 1 to 3. Y ¹ and Y ² are each independently a halogen atom. R ⁵ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

The halogen atom represented by Y ¹ and Y ^2, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable, from the viewpoint of enhancing the reaction yield. From the viewpoint of increasing the reaction yield, it is preferable that Y ¹ and Y ² have different reactivities to the —OH group in the formula (ia).

  By reacting the hydroxy compound represented by the formula (i-a) with the dihalogen compound represented by the formula (i-b) in the presence of a base such as pyridine in a solvent such as tetrahydrofuran, the formula (i) The compound represented by -c) is obtained. Compound (i′-1) is obtained by reacting this compound (ic) with (meth) acrylic acid in the presence of a base such as potassium carbonate or potassium iodide in a solvent such as dimethylformamide. be able to.

In addition, the compound (i) has, for example, a group represented by the above formula (1 ′), and L ′ is —O—L ′ ^a- (L ′ ^a is ^a divalent group containing ^a hetero atom) And in the case of the compound represented by the following formula (i'-1 ') which is a compound (i-1), according to the following scheme, it can synthesize | combine simply with sufficient yield.

In the above scheme, E ¹ , E ² and E ³ are each independently an oxygen atom or a sulfur atom. R ^{3 '} is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. n 'is an integer of 0 to 13. 'If is 2 or more, plural R ^3' n may be the same or different, two of the plurality of R ^{3 ',} are combined with each other _{-CH 2 -, - CH 2 -CH} 2 -, - It may form a C (CH ₃ ) ₂ -or -O- crosslink. R ^{4 ′} is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. L ′ ^a is a divalent linking group having a hetero atom. p ′ and q ′ are each independently an integer of 1 to 3. Y ^{1 ′} and Y ^{2 ′} are each independently a halogen atom. R ⁵ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

As a halogen atom represented by Y ^{1 '} and Y ^2' , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example. Among these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable, from the viewpoint of enhancing the reaction yield. From the viewpoint of enhancing the reaction yield, Y ^{1 ′} and Y ^{2 ′} preferably have different reactivities to —OH group in formula (i ′ a ′).

  The compound represented by the formula (m-a ') and the (thio) phosgene represented by the formula (m-b') are reacted in a solvent such as methylene chloride in the presence of a base such as pyridine or dimethylaminopyridine As a result, the hydroxy compound represented by the formula (ia ′) is obtained. The compound (i-a ') and the dihalogen compound represented by the formula (i-b') can be prepared by using acetonitrile, etc. in the presence of a base such as triethylamine or 1,4-diazabicyclo [2.2.2] octane. By reacting in a solvent, a compound represented by the formula (ic ′) is obtained. Compound (i′-1 ′) is obtained by reacting this compound (ic ′) with (meth) acrylic acid in the presence of a base such as potassium carbonate or potassium iodide in a solvent such as dimethylformamide. You can get

The compound (i-1 ′ ′) in which the compound (i) has a group represented by the above formula (1 ′), L ′ and R ^{4 ′} are both a single bond and the compound (i-1) is Base compound such as triethylamine, 1,4-diazabicyclo [2.2.2] octane, etc., and hydroxy compound represented by formula (i-a ') and (meth) acrylic acid halide such as (meth) acrylic acid chloride The compound (i′-1 ′ ′) can be obtained by reaction in a solvent such as acetonitrile below.

  The resulting product is appropriately purified by column chromatography, recrystallization, distillation or the like to obtain a compound (i'-1), a compound (i'-1 ') and a compound (i'-1 "). It can be released.

  The compound (i) other than the compound (i′-1), the compound (i′-1 ′) and the compound (i′-1 ′ ′) can also be synthesized by the same method as described above.

[Structural unit (II)]
Structural unit (II) is a structural unit represented by following formula (2). A group represented by ^-CR 15 ^R 16 ^{R 17} of the structural unit (II) is an acid-dissociable group. An "acid-dissociable group" is a group which substitutes the hydrogen atom of a carboxy group, Comprising: The group which dissociates by the effect | action of an acid is said. The sensitivity of the radiation sensitive resin composition is improved by the polymer [A] having the structural unit (II), and as a result, the LWR performance and the like can be improved.

In the above formula (2), R ¹⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ¹⁵ is a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ¹⁶ and R ¹⁷ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, or 3 to 3 carbon atoms which are combined together with the carbon atoms to which these groups are combined. 20 represents an alicyclic structure.

From the viewpoint of the copolymerizability of the monomer giving the structural unit (II), R ¹⁴ is preferably a hydrogen atom and a methyl group, more preferably a methyl group.

R ^15, examples of the monovalent hydrocarbon group ^{R 16} and having 1 to 20 carbon atoms represented by ^{R 17,} for example similar to a monovalent hydrocarbon group exemplified as ^{R 1} and ^{R 2} in the formula (1) And the like. These groups are combined with each other together with the carbon atoms to which they are attached as a cycloaliphatic ring structure composed C3-20, for example, the aforementioned formula (1) R ¹ and R ² hydrocarbon groups are those aligned with one another And the like structures and the like as those exemplified as the alicyclic structure constituted together with the carbon atom to which is attached.

  As structural unit (II), structural units represented by the following formulas (2-1) to (2-4) (hereinafter also referred to as “structural units (II-1) to (II-4)”) are preferable .

R < ¹⁴ > -R < ¹⁷ > is synonymous with the said Formula (2) in said Formula (2-1)-(2-4). i and j are each independently an integer of 1 to 4;

  Examples of the structural units (II-1) to (II-4) include structural units represented by the following formulas, and the like.

In said formula, R < ¹⁴ > is synonymous with said formula (2).

  As the structural unit (II), structural units (II-1) and (II-3) are preferable, and a structural unit derived from 1-alkyl-1-cyclopentyl (meth) acrylate, 2-cyclohexylpropan-2-yl ( Structural units derived from meta) acrylate and structural units derived from 2-alkyl-2-tetracyclodecanyl (meth) acrylate are more preferred.

  The lower limit of the content ratio of the structural unit (II) is preferably 10 mol%, more preferably 30 mol%, still more preferably 40 mol%, based on all structural units constituting the polymer [A]. As an upper limit of the said content rate, 80 mol% is preferable, 70 mol% is more preferable, and 60 mol% is more preferable. By setting the content ratio in the above range, the sensitivity of the radiation sensitive resin composition can be further improved, and as a result, the LWR performance and the like can be further improved.

[Structural unit (III)]
The structural unit (III) is a structural unit other than the structural unit (I), and is a structural unit containing a lactone structure, a cyclic carbonate structure, a sultone structure or a combination thereof. [A] The polymer can further adjust the solubility in a developer by further having the structural unit (III) in addition to the structural unit (I), and as a result, the radiation sensitive resin composition LWR performance etc. of objects can be further improved. Moreover, the adhesiveness of the resist pattern and board | substrate formed from the said radiation sensitive resin composition can be improved.

  As structural unit (III), the structural unit etc. which are represented by a following formula are mentioned, for example.

In the above formula, R ^L1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  Among these, as structural unit (III), structural units containing a norbornane lactone structure, structural units containing a γ-butyrolactone structure, structural units containing an ethylene carbonate structure and a structural unit containing a norbornane sultone structure are preferable. Structural unit derived from y-yl (meth) acrylate, structural unit derived from oxanorbornane lactone-yl (meth) acrylate, structural unit derived from cyano-substituted norbornane lactone-yl (meth) acrylate, γ-butyrolactone-yl (meth More preferred are structural units derived from acrylate, structural units derived from ethylene carbonate-ylmethyl (meth) acrylate, and structural units derived from norbornane sultone-yl (meth) acrylate.

  When the polymer [A] has the structural unit (III), the lower limit of the content ratio of the structural unit (III) is preferably 10 mol%, based on all structural units constituting the [A] polymer, The mole% is more preferable, and 30 mole% is more preferable. As a maximum of the above-mentioned content rate, 70 mol% is preferred, 60 mol% is more preferred, and 55 mol% is still more preferred. By making the said content rate into the said range, LWR performance etc. of the said radiation sensitive resin composition can be improved further. Further, the adhesion of the resist pattern to the substrate can be further improved.

[Other structural unit]
[A] The polymer may have other structural units other than the above structural units (I) to (III). Examples of other structural units include structural units containing a hydroxy group.

  As a structural unit containing a hydroxy group, the structural unit etc. which are represented by a following formula are mentioned, for example.

In the above formula, R ^L2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  As an upper limit of the content rate of the structural unit containing a hydroxy group, 60 mol% is preferable with respect to all the structural units which comprise a [A] polymer, 40 mol% is more preferable, and 20 mol% is further more preferable.

  [A] The polymer may have other structural units in addition to the structural unit containing a hydroxy group. Such other structural units include, for example, structural units containing a carboxy group, cyano group, nitro group, sulfonamide group or a combination thereof, and structural units containing a non-dissociative hydrocarbon group. As an upper limit of the content rate of these structural units, 20 mol% is preferable and 10 mol% is more preferable.

  The lower limit of the content of the polymer [A] is preferably 70% by mass, more preferably 80% by mass, with respect to the total solid content (the sum of components other than the solvent) of the radiation sensitive resin composition. % By mass is more preferred.

<[A] Synthesis Method of Polymer>
[A] The polymer can be synthesized, for example, by polymerizing monomers giving each structural unit in a suitable solvent using a radical polymerization initiator or the like.

  As a radical polymerization initiator, for example, azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropyl pro Azo-based radical initiators such as pyonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate; benzoyl peroxide, t-butyl hydroperoxide, Peroxide radical initiators, such as cumene hydroperoxide, etc. may be mentioned. Among these, AIBN and dimethyl 2,2′-azobisisobutyrate are preferred, and AIBN is more preferred. These radical polymerization initiators can be used alone or in combination of two or more.

Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and the like;
Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane;
Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene;
Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene and the like;
Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate and the like;
Ketones such as acetone, butanone, 4-methyl-2-pentanone, 2-heptanone;
Ethers such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes;
Alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2- pentanol, etc. are mentioned. The solvents used for these polymerizations may be used alone or in combination of two or more.

  As a minimum of reaction temperature in polymerization, 40 ° C is preferred and 50 ° C is more preferred. As a maximum of the above-mentioned reaction temperature, 150 ° C is preferred and 120 ° C is more preferred. As a minimum of reaction time in polymerization, 1 hour is preferred and 2 hours are more preferred. As a maximum of the above-mentioned reaction time, 48 hours are preferred and 24 hours are more preferred.

  [A] The lower limit of the polystyrene equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the polymer is preferably 1,000, more preferably 2,000, still more preferably 3,000, 000 is particularly preferred. As an upper limit of said Mw, 50,000 are preferable, 30,000 are more preferable, 20,000 is more preferable, 15,000 is especially preferable. [A] By making Mw of a polymer into the said range, the coating property of the said radiation sensitive resin composition can be improved, As a result, development defect inhibitory property can be improved more.

  [A] The upper limit of the ratio (Mw / Mn) of Mw to polystyrene-equivalent number average molecular weight (Mn) by GPC of the polymer is preferably 5, more preferably 3, more preferably 2, and particularly preferably 1.7. . The lower limit of the above ratio is usually 1 and is preferably 1.1.

Mw and Mn of the polymer in the present specification are values measured using gel permeation chromatography (GPC) under the following conditions.
GPC column: Tosoh's "G2000 HXL", 2 "G3000 H XL" and 1 "G 4000 H XL" Column temperature: 40 ° C
Elution solvent: tetrahydrofuran (Wako Pure Chemical Industries, Ltd.)
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential Refractometer Standard substance: Monodispersed polystyrene

<[B] acid generator>
[B] An acid generator is a substance that generates an acid upon exposure. The generated acid dissociates the acid dissociable group possessed by the [A] polymer and the like to generate a carboxy group and the like, and the solubility of the [A] polymer in the developing solution containing the organic solvent is lowered. As a form of containing [B] acid generator in the radiation sensitive resin composition capable of forming a resist pattern from the radiation sensitive resin composition, a form of a low molecular weight compound as described later (hereinafter referred to as “appropriately It may also be in the form of [B] an acid generator, or in the form of an acid generating group incorporated as part of a polymer, or in the form of both of them.

  Examples of the acid generator (B) include onium salt compounds, N-sulfonyloxyimide compounds, halogen-containing compounds, and diazoketone compounds.

  Examples of the onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts and the like.

  As a sulfonium salt, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1-difluoroethanesulfonate, triphenylsulfonium camphorsulfonate, 4 -Cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexyl Phenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyl Diphenyl sulfonium camphor sulfonate, 4-methanesulfonyl phenyl diphenyl sulfonium trifluoromethane sulfonate, 4-methane sulfonyl phenyl diphenyl sulfonium nonafluoro-n-butane sulfonate, 4-methane sulfonyl phenyl diphenyl sulfonium perfluoro-n-octane sulfonate, 4-methane sulfonyl Phenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluro B ethanesulfonate, 4-methanesulfonyl-phenyl camphorsulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) - hexane-1-sulfonate, and the like.

  Examples of tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona Fluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophen -Bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium camphorsulfonate , 1- (6-n-butoxynaphthalen-2-yl) Trahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydro Thiophenium perfluoro-n-octane sulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2 , 2-tetrafluoroethane sulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium camphorsulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate , 1- (3,5-dimethyl-4) Hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-) 4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, 1- (3,5-dimethyl-4-hydroxyl) And phenyl) tetrahydrothiophenium camphorsulfonate and the like.

  Examples of iodonium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2 1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t- butylphenyl) iodonium camphorsulfonate, and the like.

Examples of the N-sulfonyloxyimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoro-ethanone Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide etc. can be mentioned.

  As the acid generator (B), an acid generator represented by the following formula (3) is preferable. [B] When the acid generator has the following structure, the diffusion length of the acid generated by the exposure in the resist film is appropriately shortened due to the interaction with the structural unit (I) of the polymer [A]. As a result, LWR performance etc. of the said radiation sensitive resin composition can be improved more.

In the above formula (3), R ¹⁸ is a monovalent group containing an alicyclic structure with 6 or more ring members or a monovalent group containing an aliphatic heterocyclic structure with 6 or more ring members. R ¹⁹ is a C 1-10 fluorinated alkanediyl group. X ⁺ is a monovalent radiation-sensitive onium cation.

The monovalent group containing an alicyclic structure having 6 or more ring members, which is represented by R ¹⁸ above, is, for example, a monocyclic group such as cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, etc. Cycloalkyl group;
A monocyclic cycloalkenyl group such as cyclohexenyl group, cycloheptenyl group, cyclooctenyl group and cyclodecenyl group;
Polycyclic cycloalkyl groups such as norbornyl group, adamantyl group, tricyclodecyl group and tetracyclododecyl group;
And polycyclic cycloalkenyl groups such as norbornenyl group and tricyclodecenyl group.

Examples of the monovalent group containing an aliphatic heterocyclic structure having 6 or more ring members and represented by R ¹⁸ include, for example, a group containing a lactone structure such as a norbornane lactone-yl group;
A group containing a sultone structure such as a norbornane sultone-yl group;
An oxygen atom-containing heterocyclic group such as oxacycloheptyl group and oxanorbornyl group;
Nitrogen atom-containing heterocyclic groups such as azacyclohexyl, azacycloheptyl and diazabicyclooctane-yl;
Examples thereof include sulfur atom-containing heterocyclic groups such as thiacyclohexyl, thiacycloheptyl and thianorbornyl.

The lower limit of the number of ring members of the group represented by R ¹⁸ is preferably 8, more preferably 9, and still more preferably 10. The upper limit of the number of ring members is preferably 15, and more preferably 13. By setting the number of ring members in the above range, the diffusion length of the above-mentioned acid can be made more appropriate. As a result, the LWR performance and the like of the radiation sensitive resin composition can be further improved.

As R ¹⁸ , a monovalent group containing an alicyclic structure having 9 or more ring members and a monovalent group containing an aliphatic heterocyclic structure having 9 or more ring members are preferable, and an adamantyl group, a hydroxyadamantyl group, norbornane lactone-yl group is preferable. The group and 5-oxo-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-yl group are more preferred, and the adamantyl group is even more preferred.

As a C1-C10 fluorinated alkanediyl group represented by R ¹⁹ , for example, one or more of hydrogen atoms of a C1-C10 alkanediyl group such as methanediyl group, ethanediyl group, propanediyl group and the like can be mentioned Examples thereof include groups substituted with a fluorine atom.

The R ^19, SO ₃ ^- fluorinated alkane diyl group which has a fluorine atom to carbon atom is bonded to adjacent groups are preferred, SO ₃ ^- 2 fluorine atoms to the carbon atom adjacent to the group is attached The fluorinated alkanediyl group is more preferable, and 1,1-difluoromethanediyl group, 1,1-difluoroethanediyl group, 1,1,3,3,3-pentafluoro-1,2-propanediyl group, 1,1 Further preferred are 2,2,2-tetrafluoroethanediyl, 1,1,2,2-tetrafluorobutanediyl and 1,1,2,2-tetrafluorohexanediyl.

The monovalent radiation-sensitive onium cation represented by X ⁺ is a cation that decomposes upon irradiation with exposure light. In the exposed area, a sulfonic acid is generated from the proton generated by the decomposition of the photolytic onium cation and the sulfonate anion. Examples of the monovalent radiation-sensitive onium cation represented by X ⁺ include a cation represented by the following formula (X-1), a cation represented by the following formula (X-2), and the following formula (X-) The cation etc. which are represented by 3) are mentioned.

In the above formula (X-1), R ^a1 , R ^a2 and R ^a3 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alkyl group An aromatic hydrocarbon group having 6 to 12 carbon atoms, -OSO ₂ -R ^P or -SO ₂ -R ^Q , or a ring structure in which two or more of these groups are combined with each other . R ^P and R ^Q each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms Or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms. k1, k2 and k3 are each independently an integer of 0 to 5; When R ^{a1 to} R ^a3 and R ^P and R ^Q are each plural, the plural R ^{a1 to} R ^a3 and R ^P and R ^Q may be the same or different.

In the above formula (X-2), R ^b1 is a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 8 carbon atoms It is a group. k4 is an integer of 0 to 7; When R ^b1 is plural, plural R ^b1s may be the same or different, and plural R ^b1s may represent a ring structure configured to be combined with each other.
R ^b2 is a substituted or unsubstituted linear or branched alkyl group having 1 to 7 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 or 7 carbon atoms. k5 is an integer of 0 to 6; When R ^b2 is plural, plural R ^b2 may be the same or different, and plural R ^b2 may represent a ring structure which is combined with each other. q is an integer of 0 to 3;

In the above formula (X-3), R ^c1 and R ^c2 each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted carbon atom having 6 carbon atoms Or an aromatic hydrocarbon group, -OSO ₂ -R ^R or -SO ₂ -R ^S , or a ring structure in which two or more of these groups are combined with each other. R ^R and R ^S each independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms Or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms. k6 and k7 are each independently an integer of 0 to 5; When R ^c1 , R ^c2 , R ^R and R ^S are each plural, the plural R ^c1 , R ^c2 , R ^R and R ^S may be the same or different.

Examples of the unsubstituted linear alkyl group represented by the above R ^{a1 to} R ^a3 , R ^b1 , R ^b2 , R ^c1 and R ^c2 include, for example, a methyl group, an ethyl group, an n-propyl group and an n-butyl group Etc.

The unsubstituted branched alkyl group represented by the above R ^{a1 to} R ^a3 , R ^b1 , R ^b2 , R ^c1 and R ^c2 is, for example, an i-propyl group, an i-butyl group, a sec-butyl group, or t -Butyl group etc. are mentioned.

Examples of the unsubstituted aromatic hydrocarbon group represented by R ^{a1 to} R ^a3 , R ^c1 and R ^c2 include aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, and naphthyl group; benzyl group, Aralkyl groups such as phenethyl group can be mentioned.

As a non-substituted aromatic hydrocarbon group represented by said R ^b1 and R ^b2 , a phenyl group, a tolyl group, a benzyl group etc. are mentioned, for example.

  As a substituent which may substitute the hydrogen atom which the said alkyl group and aromatic hydrocarbon group have, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxy group, carboxy group, cyano group And a nitro group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acyl group, an acyloxy group and the like. Among these, a halogen atom is preferable, and a fluorine atom is more preferable.

As the above R ^{a1 to} R ^a3 , R ^b1 , R ^b2 , R ^c1 and R ^c2 , unsubstituted linear or branched alkyl group, fluorinated alkyl group, unsubstituted monovalent aromatic hydrocarbon group , -OSO ₂ -R "and _-SO 2 -R", more preferably a monovalent aromatic hydrocarbon group having a fluorinated alkyl group and unsubstituted, more preferably a fluorinated alkyl group. R ′ ′ is an unsubstituted monovalent alicyclic hydrocarbon group or an unsubstituted monovalent aromatic hydrocarbon group.

  As k1, k2 and k3 in Formula (X-1), the integer of 0-2 is preferable, 0 and 1 are more preferable, and 0 is more preferable. As k4 in Formula (X-2), the integer of 0-2 is preferable, 0 and 1 are more preferable, and 1 is more preferable. As k5, the integer of 0-2 is preferable, 0 and 1 are more preferable, and 0 is more preferable. As k6 and k7 in Formula (X-3), the integer of 0-2 is preferable, 0 and 1 are more preferable, and 0 is more preferable.

  Examples of the acid generator represented by the above formula (3) include compounds represented by the following formulas (3-1) to (3-12) (hereinafter, “compounds (3-1) to (3-12)” And so on).

In the above formulas (3-1) to (3-12), X ⁺ is a monovalent radiation-sensitive onium cation.

  [B] The acid generator is preferably an onium salt compound, more preferably a compound having a cation represented by the above formula (X-1) and a compound having a cation represented by the above formula (X-2), the compound (3-1), (3-2), (3-11) and (3-12) are more preferable.

  [B] When the acid generator is a [B] acid generator, the lower limit of the content of the [B] acid generator is preferably 0.1 parts by mass with respect to 100 parts by mass of the [A] polymer, 0.5 mass part is more preferable, and 1 mass part is further more preferable. As a maximum of the above-mentioned content, 30 mass parts is preferred, 20 mass parts is more preferred, and 15 mass parts is still more preferred. [B] By setting the content of the acid generator in the above range, the sensitivity and the developability of the radiation sensitive resin composition can be improved, and as a result, the LWR performance and the like can be improved. [B] The acid generator may be used alone or in combination of two or more.

<[C] Acid Diffusion Controller>
The said radiation sensitive resin composition may contain a [C] acid diffusion control body as needed. [C] The acid diffusion controller controls the diffusion phenomenon of the acid generated from the acid generator in the resist film by exposure to light [B], and has the effect of suppressing undesirable chemical reaction in the non-exposed region. Moreover, while the storage stability of a radiation sensitive resin composition improves, the resolution as a resist improves more. Furthermore, the line width change of the resist pattern due to the fluctuation of the placement time from exposure to development processing can be suppressed, and a radiation sensitive resin composition excellent in process stability can be obtained. [C] The form of containing the acid diffusion controller in the radiation sensitive resin composition may be incorporated as part of a polymer even in the form of a free compound (hereinafter referred to as “[C] acid diffusion controller” as appropriate). Or both.

  [C] As the acid diffusion control agent, for example, a compound represented by the following formula (4) (hereinafter, also referred to as “nitrogen-containing compound (I)”), a compound having two nitrogen atoms in the same molecule (hereinafter, "Nitrogen-containing compound (II)", a compound having three nitrogen atoms (hereinafter also referred to as "nitrogen-containing compound (III)"), an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, etc. Be

In the above formula (4), R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted, an aryl group or an aralkyl group. .

  Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; aromatic amines such as aniline etc. Be

  Examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ', N'-tetramethylethylenediamine and the like.

  Examples of the nitrogen-containing compound (III) include polyamine compounds such as polyethyleneimine and polyallylamine; polymers such as dimethylaminoethyl acrylamide and the like.

  Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Be

  Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like.

  Examples of nitrogen-containing heterocyclic compounds include pyridines such as pyridine and 2-methylpyridine; morpholines such as N-propylmorpholine and N- (undecylcarbonyloxyethyl) morpholine; pyrazine and pyrazole.

  A compound having an acid dissociable group can also be used as the nitrogen-containing organic compound. Examples of nitrogen-containing organic compounds having such an acid dissociable group include N-t-butoxycarbonylpiperidine, N-t-butoxycarbonylimidazole, N-t-butoxycarbonylbenzimidazole, and N-t-butoxycarbonyl-2 -Phenylbenzimidazole, N- (t-butoxycarbonyl) di-n-octylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl) diphenylamine , N-t-butoxycarbonyl-4-hydroxypiperidine, N-t-amyloxycarbonyl-4-hydroxypiperidine and the like.

  Further, as the [C] acid diffusion control agent, it is also possible to use a photodisintegrable base which is photosensitive upon exposure to generate a weak acid. As a photodisintegrable base, the onium salt compound etc. which are decomposed | disassembled by exposure and loses acid diffusion controllability are mentioned, for example. As an onium salt compound, the sulfonium salt compound represented, for example by following formula (5-1), the iodonium salt compound represented by following formula (5-2), etc. are mentioned.

R < ²³ > -R < ²⁷ > is respectively independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a halogen atom in said Formula (5-1) and Formula (5-2). E ^- and Q ^- are each ^{independently, OH -, R β -COO -} , R β -SO 3 - is an anion represented by or the following formula (5-3). However, R ^β is an alkyl group, an aryl group or an aralkyl group.

In the above formula (5-3), R ²⁸ represents a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 12 carbon atoms, or 1 carbon atom And 12 linear or branched alkoxy groups. u is an integer of 0 to 2; When u is 2, two R ²⁸ may be the same or different.

  As said photodisintegrable base, the compound etc. which are represented by a following formula are mentioned, for example.

  Among these, sulfonium salts are preferable as the photodisintegrable base, triarylsulfonium salts are more preferable, and triphenylsulfonium salicylate and triphenylsulfonium 10-camphorsulfonate are more preferable.

  When the said radiation sensitive resin composition contains a [C] acid diffusion controller as a [C] acid diffusion controller, the lower limit of the content of the [C] acid diffusion controller is the [A] polymer 0.1 mass part is preferable with respect to 100 mass parts, 0.3 mass part is more preferable, and 1 mass part is further more preferable. As a maximum of the above-mentioned content, 20 mass parts is preferred, 15 mass parts is more preferred, and 10 mass parts is still more preferred.

<[D] polymer>
The polymer [D] is a fluorine atom-containing polymer other than the polymer [A]. When the said radiation sensitive resin composition contains a [D] polymer, when the resist film is formed, its distribution is in the vicinity of the surface of the resist film due to the oil repellent feature of the fluoropolymer in the film. There is a tendency to be localized, and it is possible to suppress the elution of the acid generator, the acid diffusion control agent, and the like at the time of immersion exposure to the immersion medium. Further, the water repellent characteristics of the [D] polymer allow the advancing contact angle between the resist film and the immersion medium to be controlled within a desired range, and the occurrence of bubble defects can be suppressed. Furthermore, the receding contact angle between the resist film and the immersion medium becomes high, and high speed scan exposure becomes possible without leaving water droplets. Thus, when the said radiation sensitive resin composition contains a [D] polymer, the resist film suitable for the liquid immersion exposure method can be formed.

  The polymer [D] is not particularly limited as long as it is a polymer having a fluorine atom, but the fluorine atom content (% by mass) is higher than that of the polymer [A] in the radiation sensitive resin composition. Is preferred. [A] When the fluorine atom content rate is higher than that of the polymer, the degree of uneven distribution described above becomes higher, and the properties such as water repellency and elution suppression property of the obtained resist film are improved.

The lower limit of the fluorine atom content of the polymer [D] is preferably 1% by mass, more preferably 2% by mass, still more preferably 4% by mass, and particularly preferably 7% by mass. As an upper limit of the said fluorine atom content rate, 60 mass% is preferable, 40 mass% is more preferable, and 30 mass% is more preferable. When the fluorine atom content of the polymer [D] is less than the above lower limit, the hydrophobicity of the resist film surface may be lowered. The fluorine atom content (% by mass) of the polymer can be calculated from the structure of the polymer determined by ¹³ C-NMR spectrum measurement or the like.

  The polymer [D] preferably has the following structural unit (Da), the following structural unit (Db), and a combination thereof. [D] The polymer may have one or more structural units (Da) and one or more structural units (Db).

[Structural unit (Da)]
The structural unit (Da) is a structural unit represented by the following formula (6a). [D] The polymer can adjust the fluorine atom content by having the structural unit (Da).

In the above formula (6a), R ^D is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. G represents a single bond, an oxygen atom, a sulfur _{atom, -CO-O -, - SO} 2 -O-NH -, - is CO-NH- or -O-CO-NH-. R ^E is a C 1-6 monovalent fluorinated chain hydrocarbon group or a C 4-20 monovalent fluorinated aliphatic alicyclic hydrocarbon group.

Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 6 carbon atoms represented by R ^E include trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, and 2,2 , 3,3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoropropyl group, perfluoro n-propyl group, perfluoro i-propyl group, perfluoro n-butyl group, Perfluoro i-butyl group, perfluoro t-butyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, perfluorohexyl group etc. are mentioned.

The monovalent fluorinated alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ^E is, for example, monofluorocyclopentyl group, difluorocyclopentyl group, perfluorocyclopentyl group, monofluorocyclohexyl group, difluorocyclopentyl group, Perfluorocyclohexylmethyl group, fluoronorbornyl group, fluoroadamantyl group, fluorobornyl group, fluoroisobornyl group, fluorotricyclodecyl group, fluorotetracyclodecyl group and the like can be mentioned.

  As a monomer giving the structural unit (Da), for example, trifluoromethyl (meth) acrylic acid ester, 2,2,2-trifluoroethyl (meth) acrylic acid ester, 2,2,2-trifluoroethyloxy Carbonyl methyl (meth) acrylic ester, perfluoroethyl (meth) acrylic ester, perfluoro n-propyl (meth) acrylic ester, perfluoro i-propyl (meth) acrylic ester, perfluoro n-butyl (meth) ) Acrylic acid ester, perfluoro i-butyl (meth) acrylic acid ester, perfluoro t-butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) ) Acrylic acid ester, 1- (2,2,3,3,4,4,5,5-octafluorope (Tyl) (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 1- (2,2,3,3,3-pentafluoropropyl) (meth) acrylate, monofluorocyclopentyl (meth) Acrylic acid ester, difluorocyclopentyl (meth) acrylic acid ester, perfluorocyclopentyl (meth) acrylic acid ester, monofluorocyclohexyl (meth) acrylic acid ester, difluorocyclopentyl (meth) acrylic acid ester, perfluorocyclohexylmethyl (meth) acrylic acid Acid ester, fluoro norbornyl (meth) acrylic ester, fluoro adamantyl (meth) acrylic ester, fluoro bornyl (meth) acrylic ester, fluoroisobornyl (meta Acrylic acid esters, fluoro tricyclodecyl (meth) acrylate, fluoro tetracyclododecene decyl (meth) acrylic acid ester. Among these, 2,2,2-trifluoroethyloxycarbonylmethyl (meth) acrylic acid ester is preferable.

  [D] When the polymer has a structural unit (Da), the lower limit of the content ratio of the structural unit (Da) is preferably 5 mol%, based on all structural units constituting the [D] polymer, and 10 The mole% is more preferable, and 20 mole% is more preferable. As an upper limit of the said content rate, 95 mol% is preferable, 75 mol% is more preferable, and 40 mol% is more preferable. By using such a content ratio, a higher dynamic contact angle of the resist film surface can be exhibited at the time of immersion exposure.

[Structural unit (Db)]
The structural unit (Db) is a structural unit represented by the following formula (6b). [D] The polymer has high hydrophobicity by having the structural unit (Db), so that the dynamic contact angle of the resist film surface formed of the radiation sensitive resin composition can be further improved.

In the above formula (6b), ^RF is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ²⁹ is a (S + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, -NR′-, a carbonyl group, -CO-O- or an end on the R ³⁰ side of R ²⁹ It also includes those having a structure in which -CO-NH- is bonded. R ′ is a hydrogen atom or a monovalent organic group. R ³⁰ is a single bond, a divalent C 1-10 linear hydrocarbon group, or a C 4-20 divalent alicyclic hydrocarbon group. X ² is a divalent chain fluorinated hydrocarbon group having 1 to 20 carbon atoms. A ¹ represents an oxygen atom, -NR "-, - CO- O- * or _-SO 2 -O- * .R" is a hydrogen atom or a monovalent organic group. * ^Indicates a binding site that binds to ^{R 31.} R ³¹ is a hydrogen atom or a monovalent organic group. s is an integer of 1 to 3; However, when s is 2 or 3, several R <^30> , X < ² >, A < ¹ > and R <^31> may be same or different, respectively.

When R ³¹ is a hydrogen atom, it is preferable in that the solubility of the polymer [D] in an alkali developer can be improved.

Examples of the monovalent organic group represented by R ³¹ include an acid-dissociable group, an alkali-dissociable group, and a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

  Examples of the structural unit (Db) include structural units represented by the following formulas (6b-1) to (6b-3), and the like.

R29 ^' is a C1-C20 bivalent linear, branched or cyclic saturated or unsaturated hydrocarbon group in said Formula (6 b-1)-(6 b-3). R ^F , X ² , R ³¹ and s are as defined in the above formula (6b). When s is 2 or 3, the plurality of X ² and R ³¹ may be the same or different.

  When the polymer [D] has a structural unit (6b), the lower limit of the content ratio of the structural unit (6b) is preferably 5 mol%, based on all structural units constituting the [D] polymer, and 10 The mole% is more preferable, and 15 mole% is more preferable. As an upper limit of the said content rate, 90 mol% is preferable, 85 mol% is more preferable, and 80 mol% is more preferable. By setting it as such a content ratio, the resist film surface formed from the said radiation sensitive resin composition can improve the fall degree of a dynamic contact angle in alkali image development.

[Structural unit (Dc)]
[D] The polymer may have a structural unit containing an acid dissociable group (hereinafter, also referred to as “structural unit (Dc)”), in addition to the structural units (Da) and (Db) (however, , Except for those applicable to structural units (Db)). [D] When the polymer has a structural unit (Dc), the shape of the obtained resist pattern becomes better. As a structural unit (Dc), structural unit (II) etc. in the above-mentioned [A] polymer are mentioned.

  When the polymer [D] has a structural unit (Dc), the lower limit of the content ratio of the structural unit (Dc) is preferably 5 mol%, and 25 mol% with respect to all structural units constituting the [D] polymer. % Is more preferable, and 60 mol% is further preferable. As an upper limit of the said content rate, 90 mol% is preferable, 80 mol% is more preferable, and 75 mol% is more preferable.

[Other structural unit]
In addition to the above structural units, the polymer [D] may, for example, be a structural unit containing an alkali-soluble group, a structural unit containing a lactone structure, a cyclic carbonate structure, a sultone structure or a combination thereof, and an alicyclic group. You may have other structural units, such as a unit. As said alkali-soluble group, a carboxy group, sulfonamide group, a sulfo group etc. are mentioned, for example. Examples of the structural unit containing a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof include the structural unit (III) and the like in the above-mentioned [A] polymer.

  As an upper limit of the content rate of another structural unit, 30 mol% is preferable with respect to all the structural units which comprise a [D] polymer, and 20 mol% is more preferable.

  When the said radiation sensitive resin composition contains a [D] polymer, as a minimum of content of a [D] polymer, 0.5 mass part carries out to 100 mass parts of a [A] polymer. Preferably, 1 part by mass is more preferable, and 2 parts by mass is more preferable. As a maximum of the above-mentioned content, 20 mass parts is preferred, 15 mass parts is more preferred, and 10 mass parts is still more preferred.

<[E] solvent>
The radiation sensitive resin composition usually contains an [E] solvent. The solvent [E] is not particularly limited as long as it is a solvent capable of dissolving or dispersing at least the polymer [A], the acid generator [B] and the acid diffusion controller [C] optionally contained.

  [E] Examples of the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents and the like.

Examples of alcohol solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol Sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethyl nonyl alcohol, sec-tetradecyl alcohol, sec Monoalcohol solvents such as heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc.
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 -Polyhydric alcohol solvents such as ethyl 1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether.

Examples of ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether and dibutyl ether;
Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran;
Examples thereof include aromatic ring-containing ether solvents such as diphenyl ether and anisole (methyl phenyl ether).

Examples of ketone solvents include acetone, butanone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone (methyl-n-pentyl ketone), ethyl-n-butyl ketone Chain ketone solvents such as methyl-n-hexyl ketone, di-iso-butyl ketone and trimethylnonanone:
Cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone:
2,4-pentanedione, acetonylacetone, acetophenone etc. are mentioned.

Examples of the amide solvents include cyclic amide solvents such as N, N′-dimethylimidazolidinone, N-methylpyrrolidone and the like;
Examples thereof include chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide and the like.

As ester solvents, for example, methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, i-pentyl acetate, sec-acetate Acetic acid ester solvents such as pentyl, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl acetate cyclohexyl, n-nonyl acetate and the like;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Polyhydric alcohol partial ether acetate solvents such as acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate;
Carbonate solvents such as dimethyl carbonate and diethyl carbonate;
Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, ethyl lactate And n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

Examples of hydrocarbon solvents include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane , Aliphatic hydrocarbon solvents such as methylcyclohexane;
Aromatics such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.

  Among these, ester solvents and ketone solvents are preferable, polyhydric alcohol partial ether acetate solvents and cyclic ketone solvents are more preferable, and propylene glycol monomethyl ether acetate and cyclohexanone are more preferable. The said radiation sensitive resin composition may contain 1 type, or 2 or more types of [E] solvent.

<Other optional components>
The said radiation sensitive resin composition may contain the other arbitrary components besides said [A]-[E]. Examples of the other optional components include a localization promoter, a surfactant, an alicyclic skeleton-containing compound, and a sensitizer. These other optional components may be used alone or in combination of two or more.

[Distribution promoter]
The uneven distribution promoting agent has an effect of segregating the [D] polymer on the resist film surface more efficiently, for example, when the radiation sensitive resin composition contains the [D] polymer. By adding the uneven distribution accelerator to the radiation sensitive resin composition, the amount of the polymer [D] added can be smaller than that of the prior art. Therefore, the elution of the component from the resist film to the immersion liquid can be further suppressed without impairing the resolution, LWR performance, development defect suppression property, etc., or immersion exposure can be performed at high speed by high-speed scan. As a result, it is possible to improve the hydrophobicity of the surface of the resist film that suppresses immersion-induced defects such as watermark defects. As a substance that can be used as such a localized distribution accelerator, there can be mentioned a low molecular weight compound having a relative dielectric constant of 30 or more and 200 or less and a boiling point at 1 atmospheric pressure of 100 ° C. or more. Specific examples of such compounds include lactone compounds, carbonate compounds, nitrile compounds, polyhydric alcohols and the like.

  Examples of lactone compounds include γ-butyrolactone, valerolactone, mevalonic lactone, norbornane lactone and the like. As a carbonate compound, a propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate etc. are mentioned, for example. Examples of the nitrile compound include succinonitrile and the like. Examples of polyhydric alcohols include glycerin and the like.

  When the radiation sensitive resin composition contains a localization promoting agent, the lower limit of the content of the localization promoting agent is 10 parts by mass with respect to 100 parts by mass of the total amount of polymers in the radiation sensitive resin composition. A part is preferable, 15 mass parts is more preferable, 20 mass parts is more preferable, 25 mass parts is especially preferable. As a maximum of the above-mentioned content, 500 mass parts is preferred, 300 mass parts is more preferred, 200 mass parts is still more preferred, and 100 mass parts is especially preferred.

[Surfactant]
Surfactants have the effect of improving coatability, striation, developability and the like. As surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol di Nonionic surfactants such as stearate; as commercial products, KP 341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 1; 75, the same No. 95 (above, Kyoeisha Chemical Co., Ltd.), F-top EF301, the same EF303, the same EF 352 (above, Tokem Products), Megafac F171, the same F173 (above, DIC), Florard FC430, the same FC431 (above, Sumitomo 3M) , Asahi Guard AG 710, Surfron S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Industry Co., Ltd., etc.) It can be mentioned. As a maximum of content of surfactant, 2 mass parts is preferred to 100 mass parts of [A] polymer.

[Alicyclic skeleton-containing compound]
The alicyclic skeleton-containing compound has an effect of improving dry etching resistance, pattern shape, adhesion to a substrate, and the like.

Examples of alicyclic skeleton-containing compounds include adamantane derivatives such as 1-adamantane carboxylic acid, 2-adamantanone, and t-butyl 1-adamantane carboxylic acid;
Deoxycholic acid esters such as t-butyl deoxycholic acid, t-butoxycarbonylmethyl deoxycholic acid, 2-ethoxyethyl deoxycholic acid;
Lithocholic acid esters such as t-butyl lithocholic acid, t-butoxycarbonyl methyl lithocholic acid, 2-ethoxyethyl lithocholic acid;
3- [2-hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 ^2,5 . ^17,10 ] dodecane, 2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] nonane and the like. The upper limit of the content of the alicyclic skeleton-containing compound in the radiation sensitive resin composition is preferably 5 parts by mass with respect to 100 parts by mass of the polymer [A].

[Sensitizer]
The sensitizer has an effect of increasing the amount of acid generated from the acid generator or the like [B], and has an effect of improving the "apparent sensitivity" of the radiation sensitive resin composition.

  Examples of the sensitizer include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. As an upper limit of content of the sensitizer in the said radiation sensitive resin composition, 2 mass parts is preferable with respect to 100 mass parts of [A] polymer.

<Method of Preparing Radiation-Sensitive Resin Composition>
The said radiation sensitive resin composition mixes the [A] polymer, the [B] acid generator, the [C] acid diffusion controlling agent etc. which are contained as needed, and the [E] solvent in a predetermined ratio, for example It can be prepared by The radiation sensitive resin composition is preferably filtered, for example, with a filter having a pore diameter of about 0.2 μm after mixing. As a minimum of solid content concentration of the radiation sensitive resin composition concerned, 0.1 mass% is preferred, 0.5 mass% is more preferred, and 1 mass% is still more preferred. As an upper limit of the said solid content concentration, 50 mass% is preferable, 30 mass% is more preferable, and 10 mass% is more preferable.

<Method for forming resist pattern>
The method for forming a resist pattern includes a step of forming a resist film (hereinafter, also referred to as “resist film formation step”), a step of exposing the resist film (hereinafter, also referred to as “exposure step”), and the exposed resist A step of developing the film (hereinafter, also referred to as a “development step”) is provided. In the said resist pattern formation method, the said resist film is formed with the said said radiation sensitive resin composition.

  According to the resist pattern forming method, since the above-mentioned radiation sensitive resin composition is used, LWR is small and resolution is high while exhibiting excellent depth of focus, MEEF performance and film shrinkage suppressing property. It is possible to form a resist pattern which is excellent in rectangular shape and less in development defects. Each step will be described below.

[Resist film formation process]
At this process, a resist film is formed using the said radiation sensitive resin composition. Examples of the substrate on which the resist film is formed include conventionally known substrates such as silicon wafers, wafers coated with silicon dioxide, and aluminum. Further, for example, an organic or inorganic antireflective film disclosed in Japanese Patent Publication No. 6-12452 or Japanese Patent Laid-Open Publication No. 59-93448 may be formed on a substrate. Examples of the coating method include spin coating (spin coating), cast coating, roll coating and the like. After application, prebaking (PB) may be performed to volatilize the solvent in the coating, if necessary. As a minimum of temperature of PB, 60 ° C is preferred and 80 ° C is more preferred. As a maximum of the above-mentioned temperature, 140 ° C is preferred and 120 ° C is more preferred. As a minimum of time of PB, 5 seconds are preferred and 10 seconds are more preferred. As a minimum of the above-mentioned time, 600 seconds are preferred and 300 seconds are more preferred. The lower limit of the average thickness of the resist film to be formed is preferably 10 nm, more preferably 20 nm. As an upper limit of the said average thickness, 1,000 nm is preferable and 500 nm is more preferable.

  In the case of performing immersion exposure, when the radiation sensitive resin composition does not contain a water repellent polymer additive, etc., the immersion liquid and the resist film are directly formed on the resist film formed above. In order to avoid contact, a protective film for immersion that is insoluble in the immersion liquid may be provided. As a liquid immersion protective film, a solvent peelable protective film (see JP-A-2006-227632) which is peeled off by a solvent before the development step, a developer peelable protective film which peels simultaneously with the development of the development step Any of 2005/069076 and WO 2006/035790 may be used. However, from the viewpoint of throughput, it is preferable to use a developer peeling type liquid immersion protective film.

[Exposure process]
In this step, the resist film formed in the resist film forming step is exposed to light by irradiating exposure light through a photomask (in some cases, through an immersion medium such as water). The exposure light may be, for example, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), electromagnetic waves such as X-rays or γ-rays; charged particle rays such as electron beams or α-rays according to the line width of the target pattern. Etc. Among these, far ultraviolet rays, EUV and electron beam are preferable, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV and electron beam are more preferable, ArF excimer laser light, EUV and electron beam are More preferable.

  When the exposure is carried out by immersion exposure, examples of the immersion liquid to be used include water, a fluorine-based inert liquid, and the like. The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a temperature coefficient of refractive index as small as possible to minimize distortion of the optical image projected onto the film, but the exposure light source is particularly preferably ArF. In the case of excimer laser light (wavelength 193 nm), it is preferable to use water from the viewpoints of easy availability and easy handling in addition to the above-mentioned viewpoints. When water is used, additives which increase the surface activity and reduce the surface tension of water may be added in a small proportion. It is preferable that this additive does not dissolve the resist film on the wafer and that the influence on the optical coat on the lower surface of the lens can be ignored. Distilled water is preferred as water to be used.

  After the exposure, post-exposure baking (PEB) is performed, and in the exposed part of the resist film, the acid dissociable group possessed by the polymer [A] and the like by the acid generated from the acid generator and the like [B] by exposure. It is preferable to promote dissociation. This PEB can increase the difference in solubility in the developer between the exposed area and the unexposed area. As a minimum of temperature of PEB, 50 ° C is preferred and 80 ° C is more preferred. As a maximum of the above-mentioned temperature, 180 ° C is preferred and 130 ° C is more preferred. As a minimum of time of PEB, 5 seconds are preferred and 10 seconds are more preferred. As a maximum of the above-mentioned time, 600 seconds are preferred and 300 seconds are more preferred.

[Development process]
In this process, the resist film exposed in the exposure process is developed. Thereby, a predetermined resist pattern can be formed. After development, washing with a rinse solution such as water or alcohol is generally followed by drying. The developing method in the developing step may be alkaline development or organic solvent development.

  In the case of alkali development, examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n- Propylamine, triethylamine, methyl diethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1 The aqueous alkali solution etc. which dissolved at least 1 sort (s) of alkaline compounds, such as 5-diazabicyclo- [4.3.0] -5- nonene, etc. are mentioned. Among these, TMAH aqueous solution is preferable and 2.38 mass% TMAH aqueous solution is more preferable.

  In the case of organic solvent development, examples of the developer include hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, organic solvents such as alcohol solvents, and solvents containing the above organic solvents. As said organic solvent, 1 type (s) or 2 or more types of the solvent listed as an [E] solvent of the above-mentioned radiation sensitive resin composition, etc. are mentioned, for example. Among these, ester solvents and ketone solvents are preferable. As an ester solvent, an acetic acid ester solvent is preferable, and n-butyl acetate is more preferable. As a ketone solvent, a chain ketone is preferable, and 2-heptanone is more preferable. The lower limit of the content of the organic solvent in the developer is preferably 80% by mass, more preferably 90% by mass, still more preferably 95% by mass, and particularly preferably 99% by mass. As components other than the organic solvent in a developing solution, water, a silicone oil, etc. are mentioned, for example.

  As a developing method, for example, a method of immersing a substrate in a bath filled with a developer for a certain time (dip method), a method of raising a developer on the substrate surface by surface tension and developing by standing for a certain time (paddle method A method of spraying a developer onto the substrate surface (spray method), a method of continuously coating a developer onto a substrate rotating at a constant speed while scanning a developer coating nozzle at a constant speed (dynamic dispense method) Etc.

<Polymer>
The said polymer is a polymer which has a structural unit containing group represented by said Formula (1) or (1 '). Since the said polymer has the above-mentioned property, it can be used suitably as a polymer component of the said radiation sensitive resin composition, The radiation sensitive resin composition containing this has LWR performance, resolution, It is excellent in the rectangularity of the cross-sectional shape, the depth of focus, the MEEF performance, the development defect suppressing property and the film shrinkage suppressing property.

<Compound>
The said compound is a compound containing the group represented by the said Formula (1) or (1 '). Since the said compound has the above-mentioned property, it can be used suitably as a raw material monomer of the said polymer.

  The said polymer and the said compound are demonstrated by the term of said [A] polymer.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples. Each measurement in the examples was performed by the following method.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]
Using Tosoh GPC column ("G2000HXL" two, "G3000HXL" one and "G4000HXL" one), flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, sample concentration: 1.0% by mass, sample Injection amount: 100 μL, column temperature: 40 ° C., detector: Measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of a differential refractometer. Moreover, dispersion degree (Mw / Mn) was computed from the measurement result of Mw and Mn.

[ ¹³ C-NMR analysis]
Using a nuclear magnetic resonance apparatus (“JNM-ECX400” manufactured by JEOL Ltd.) and using deuterated chloroform as the measurement solvent, an analysis was performed to determine the content ratio (mol%) of the structural unit of the polymer.

<Synthesis of Compound>
[Example 1] (Synthesis of Compound (M-1))
In a 500 mL round bottom flask, 20.0 g (93.4 mmol) of (m-1), 11.1 g (140 mmol) of pyridine and 100 mL of tetrahydrofuran were added and stirring was started at room temperature. Thereto, 12.7 g (112.1 mmol) of chloroacetyl chloride was slowly dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and then heated and stirred at 50 ° C for 8 hours. After the solvent was distilled off, ethyl acetate was added and the insoluble component was removed by filtration. After washing twice with water, it was dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was purified by column chromatography to obtain 22.3 g (yield 82%) of (m-2). Next, 9.9 g (115 mmol) of methacrylic acid, 19.1 g (138 mmol) of potassium carbonate, 7.64 g (46.0 mmol) of potassium iodide and 80 mL of dimethylformamide were added to a 500 mL round bottom flask and stirred at room temperature for 30 minutes. . A solution of 22.3 g (76.7 mmol) of (m-2) in 40 mL of dimethylformamide was slowly added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. After adding ethyl acetate, washing with water was carried out four times. After drying over anhydrous sodium sulfate, the solvent was distilled off. Purification by column chromatography gave 19.8 g (yield 76%) of (M-1).

[Examples 2 to 15] (Synthesis of Compounds (M-2) to (M-15))
By appropriately selecting the precursor and performing the same operation as in Example 1, the compounds represented by the following formulas (M-2) to (M-15) were synthesized.

[Example 16] (Synthesis of Compound (M-16))
Add 20.00 g (115 mmol) of (m-3), 20.03 g (253 mmol) of pyridine, 1.41 g (11.5 mmol) of dimethylaminopyridine and 200 mL of methylene chloride to a 500 mL round bottom flask and start stirring at 0 ° C. did. Thereto, 14.54 g (126.5 mmol) of thiophosgene was slowly dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours and then extracted by adding 1 M aqueous hydrochloric acid. The obtained organic layer was washed with water twice and dried over anhydrous sodium sulfate. After distilling off the solvent, purification by column chromatography gave 13.41 g (yield 54%) of (m-4). Next, in a 500 mL round bottom flask, 13.41 g (62.1 mmol) of (m-4), 6.28 g (62.1 mmol) of triethylamine, 0.70 g of 1,4-diazabicyclo [2.2.2] octane 6.21 mmol) and 120 mL of acetonitrile were added and stirred at room temperature for 30 minutes. Thereto, 9.69 g (93.2 mmol) of methacrylic acid chloride was slowly dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. After adding ethyl acetate, washing with water was carried out four times. After drying over anhydrous sodium sulfate, the solvent was distilled off. Purification by column chromatography gave (M-16) 22.5 g (yield 69%).

[Examples 17 to 21] (Synthesis of Compounds (M-17) to (M-21))
The precursor was suitably selected and the operation represented by the following formulas (M-17) to (M-21) was synthesized by performing the same operation as in Example 16.

<Synthesis of [A] Polymer and [D] Polymer>
The monomers used for the synthesis of the [A] polymer and the [D] polymer are shown below.

[[A] Synthesis of Polymer]
[Example 22] (Synthesis of polymer (A-1))
Compound (M'-2) 8.88 g (50 mol%), compound (M'-1) 8.04 g (40 mol%), compound (M-1) 3.08 g (10 mol%) 2-butanone A monomer solution was prepared by dissolving in 40 g and adding 0.74 g of AIBN (5 mol% with respect to the total monomers) as an initiator. Next, a 100 mL three-necked flask containing 20 g of 2-butanone was purged with nitrogen for 30 minutes, heated to 80 ° C. with stirring, and the above prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The start of dropwise addition was taken as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization reaction, the polymerization solution was water-cooled and cooled to 30 ° C. or less. The cooled polymerization solution was charged into 400 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 80 g of methanol, filtered, and dried at 50 ° C. for 17 hours to synthesize a white powdery polymer (A-1) (15.7 g, yield 79) %). Mw of polymer (A-1) was 7,400, and Mw / Mn was 1.54. As a result of ¹³ C-NMR analysis, the content ratio of each structural unit derived from (M′-2), (M′-1) and (M-1) is 50.1 mol% and 40.2 mol%, respectively. , 9.7 mol%.

[Examples 23 to 44 and 46 to 49 and Synthesis Examples 1 to 3] (Polymers (A-2) to (A-23) and (A-25) to (A-28) and (CA-1) to Synthesis of (CA-3))
Polymers (A-2) to (A-23) and (A-25) to (A-28) are obtained by performing the same operation as in Example 22 except that the monomers shown in Table 1 below are used. And (CA-1) to (CA-3) were synthesized.

[Example 45] (Synthesis of Polymer (A-24))
41.88 g (50 mol%) of compound (M'-3), 40.55 g (40 mol%) of compound (M'-2), 17.58 g (10 mol%) of compound (M-1) AIBN 4 as an initiator After dissolving 24 g (5 mol% with respect to all monomers) and 1, 14 g of t-dodecyl mercaptan in 100 g of propylene glycol monomethyl ether, keep the reaction temperature at 70 ° C. for 16 hours under a nitrogen atmosphere for 16 hours. It was polymerized. After completion of the polymerization reaction, the polymerization solution was dropped into 1,000 g of n-hexane to coagulate and purify the polymer. Next, 150 g of propylene glycol monomethyl ether was added again to the above polymer, and 150 g of methanol, 34 g of triethylamine and 6 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After completion of the reaction, the solvent and triethylamine are distilled off under reduced pressure, and the obtained polymer is dissolved in 150 g of acetone and then dropped into 2,000 g of water to coagulate it, and the formed white powder is filtered at 50.degree. After drying for a while, a white powdery polymer (A-24) was obtained (62.1 g, yield 70%). The Mw of the polymer (A-24) was 7200, and the Mw / Mn was 1.88. As a result of ¹³ C-NMR analysis, the content ratio of each structural unit derived from p-hydroxystyrene, (M′-2) and (M-1) is 50.2 mol%, 40.1 mol%, 9 It was .7 mol%.

[Example 50] (Synthesis of Polymer (A-29))
A polymer (A-29) was synthesized by performing the same operation as in Example 45 except that the monomers shown in the following Table 1 were used.

  Table 1 below shows the content ratio (mol%) of each structural unit, the yield (%), the Mw and the Mw / Mn of the synthesized polymers.

[Synthesis of [[D] polymer]]
Synthesis Example 4 Synthesis of Polymer (D-1)
71.67 g (70 mol%) of a compound (M'-12) and 28.33 g (30 mol%) of a compound (M'-13) are dissolved in 100 g of 2-butanone, and dimethyl 2,2 'is used as an initiator. -A monomer solution was prepared by dissolving 6.47 g (5 mol% relative to the total monomers) of azobisisobutyrate. Next, a 1,000 mL three-necked flask containing 100 g of 2-butanone was purged with nitrogen for 30 minutes, heated to 80 ° C. with stirring, and the above prepared monomer solution was added dropwise over 3 hours using a dropping funnel . The start of dropwise addition was taken as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization reaction, the polymerization solution was water-cooled and cooled to 30 ° C. or less. The reaction solution was transferred to a 2 L separatory funnel, and then the polymerization solution was uniformly diluted with 150 g of n-hexane, and 600 g of methanol was added and mixed. Next, 30 g of distilled water was added, and the mixture was further stirred and allowed to stand for 30 minutes. Thereafter, the lower layer was recovered to obtain a propylene glycol monomethyl ether acetate solution containing the solid content of the polymer (D-1) (yield: 60%). Mw of polymer (D-1) was 7,200, and Mw / Mn was 2.00. As a result of ¹³ C-NMR analysis, the content ratio of each structural unit derived from (M′-12) and (M′-13) was 71.1 mol% and 28.9 mol%, respectively.

<Preparation of radiation sensitive resin composition>
The [B] acid generator, the [C] acid diffusion control agent, and the [E] solvent used for preparation of the radiation sensitive resin composition are shown below.

[[B] acid generator]
Each structural formula is shown below.
B-1: triphenylsulfonium 2- (adamantan-1-ylcarbonyloxy) -1,1,3,3,3-pentafluoropropane-1-sulfonate B-2: triphenylsulfonium norbornane sulton-2-yloxy Carbonyl difluoromethane sulfonate B-3: Triphenylsulfonium 3- (piperidin-1-ylsulfonyl) -1,1,2,2,3,3-hexafluoropropane-1-sulfonate B-4: triphenylsulfoniumadamantane 1-Iloxycarbonyldifluoromethanesulfonate

[[C] acid diffusion control agent]
Each structural formula is shown below.
C-1: Triphenylsulfonium salicylate C-2: Triphenylsulfonium 10-camphorsulfonate C-3: N- (n-undecane-1-ylcarbonyloxyethyl) morpholine C-4: 2, 6-dii -Propylaniline C-5: tri n-pentylamine

[[E] solvent]
E-1: Propylene glycol monomethyl ether acetate E-2: Cyclohexanone

[[F] uneven distribution promoter]
F-1: γ-butyrolactone

[Preparation of radiation sensitive resin composition for ArF exposure]
[Example 51]
[A] 100 parts by mass of (A-1) as a polymer, 8.5 parts by mass of (B-1) as a [B] acid generator, (C-1) 2 as a [C] acid diffusion control agent .3 parts by mass, (D-1) 3 parts by mass as the [D] polymer, (E-1) 2,240 parts by mass as the [E] solvent, and (E-2) 960 parts by mass, and [F] The radiation sensitive resin composition (J-1) was prepared by blending 30 parts by mass of (F-1) as a distribution promoting agent and filtering with a membrane filter having a pore size of 0.2 μm.

[Examples 52 to 80 and Comparative Examples 1 to 3]
Radiation-sensitive resin compositions (J-2) to (J-30) and (CJ-1) operated in the same manner as in Example 40 except that each component of the type and blending amount shown in Table 2 below was used ~ (CJ-3) was prepared.

<Formation of resist pattern (1)>
After applying a composition for formation of the lower layer antireflective film ("ARC 66" of Brewer Science Co., Ltd.) on a 12-inch silicon wafer surface using a spin coater ("CLEAN TRACK ACT 12" of Tokyo Electron Ltd.), 205.degree. By heating for 60 seconds to form a lower antireflective film having an average thickness of 105 nm. Each of the radiation sensitive resin compositions prepared above was applied onto the lower antireflective film using the above-mentioned spin coater, and PB was performed at 90 ° C. for 60 seconds. Then, it cooled at 23 degreeC for 30 second, and formed the resist film with an average thickness of 90 nm. Next, using the ArF excimer laser immersion exposure apparatus ("NSR-S610C" manufactured by NIKON), this resist film is used under the optical conditions of NA = 1.3 and a dipole (sigma 0.977 / 0.782) The light was exposed through a 40 nm line and space (1L1S) mask pattern. After exposure, PEB was performed at 90 ° C. for 60 seconds. Thereafter, alkali development was performed using a 2.38% by mass TMAH aqueous solution as an alkali developer, washed with water, and dried to form a positive resist pattern. When this resist pattern is formed, the exposure amount at which the line width formed through a 1-to-1 line-and-space mask with a target size of 40 nm is formed on a 1-to-1 line-and-space with a 40 nm line width is the optimum exposure amount. did.

<Formation of resist pattern (2)>
A negative resist pattern is operated in the same manner as in the formation of the resist pattern (1) except that the organic solvent is developed using n-butyl acetate instead of the aqueous solution of TMAH and washing with water is not performed. Formed.

<Evaluation>
Each radiation sensitive resin composition was evaluated by measuring according to the following method about the formed said resist pattern. A scanning electron microscope ("CG-4100" manufactured by Hitachi High-Technologies Corporation) was used to measure the resist pattern. The evaluation results are shown in Table 3 below.

[LWR performance]
The resist pattern was observed from the top of the pattern using the scanning electron microscope. The line width was measured at a total of 50 points at arbitrary points, and a 3-sigma value was obtained from the distribution of the measured values, and this was taken as LWR performance (nm). LWR performance shows that the smaller the value, the better. The LWR performance can be judged as “good” when it is 4.00 nm or less, and “defect” when it exceeds 4.00 nm.

[Resolution]
The dimension of the smallest resist pattern resolved at the above optimum exposure amount was measured, and this measurement value was defined as the resolution (nm). The lower the value of resolution, the better. The resolution can be judged as "good" when it is 34 nm or less, and "defect" when it exceeds 34 nm.

[Rectangularity of cross-sectional shape]
The cross-sectional shape of the resist pattern resolved at the above optimum exposure amount is observed, the line width Lb at the middle of the resist pattern and the line width La at the top of the film are measured, and La / Lb is calculated. Index of rectangularity. The rectangularity of the cross-sectional shape is “good” when 0.90 ≦ La / Lb ≦ 1.10, and “bad” when La / Lb <0.90 or 1.10 <La / Lb. It can be evaluated.

[Depth of focus]
In the resist pattern resolved at the above optimal exposure dose, observe the dimension when changing the focus in the depth direction, and the depth direction where the pattern dimension falls within 90% to 110% of the standard without any bridge or residue The degree of margin was measured, and this measured value was taken as the depth of focus (nm). The larger the depth of focus, the better. The depth of focus can be evaluated as "good" when it is 50 nm or more and "bad" when it is less than 50 nm.

[MEEF performance]
In the above optimum exposure dose, a resist pattern is resolved with five mask sizes (38.0 nm Line / 80 nm pitch, 39.0 nm Line / 80 nm pitch, 40.0 nm Line / 80 nm pitch, 41.0 nm Line / 80 nm pitch, 42.0 nm Line / 80 nm pitch) The line width was measured. The obtained measured values are plotted with the horizontal axis representing the mask size and the vertical axis representing the line width formed by each mask size, and the slope of the approximate straight line calculated by the least squares method is determined, and this slope is taken as the MEEF performance. The MEEF performance shows that the smaller the value, the better. The MEEF performance can be evaluated as "good" when it is 4.00 or less, and as "defect" when it exceeds 4.00.

[Development defect controllability]
The number of defects in the resist pattern resolved at the above optimum exposure amount was measured using a defect inspection apparatus (“KLA 2810” manufactured by KLA-Tencor Corporation). Then, the measured defects were classified into those judged to be derived from the resist film and foreign substances derived from the outside, and the number (pieces / cm ² ) of those judged to be derived from the resist film was calculated. The development defect inhibition property indicates that the smaller the value, the better. The development defect inhibition property can be evaluated as “good” when it is 0.1 piece / cm ² or less, and “defect” when it exceeds 0.1 piece / cm ² .

[Membrane contraction inhibitory property]
After applying a composition for formation of the lower layer antireflective film ("ARC 66" of Brewer Science Co., Ltd.) on a 12-inch silicon wafer surface using a spin coater ("CLEAN TRACK ACT 12" of Tokyo Electron Ltd.), 205.degree. By heating for 60 seconds to form a lower antireflective film having an average thickness of 105 nm. Each of the radiation sensitive resin compositions prepared above was applied onto the lower antireflective film using the above-mentioned spin coater, and PB was performed at 90 ° C. for 60 seconds. Then, it cooled at 23 degreeC for 30 second, and formed the resist film with an average thickness of 90 nm. Next, the resist film was exposed on the entire surface at 70 mJ using an ArF excimer laser liquid immersion exposure apparatus (“NSR-S610C” manufactured by NIKON), and film thickness measurement was performed to determine an average thickness A. Subsequently, after performing PEB at 90 ° C. for 60 seconds, film thickness measurement was performed again to determine an average thickness B. At this time, 100 × (A−B) / A (%) was determined, and this was taken as the membrane contraction inhibitory property. The membrane contraction inhibitory property indicates that the smaller the value, the better. The membrane contraction inhibitory property can be judged as "good" in the case of 15% or less, and "defective" in the case of exceeding 15%.

[Preparation of radiation sensitive resin composition for electron beam exposure]
[Embodiment 81]
[A] 100 parts by mass of (A-1) as a polymer, 20 parts by mass of (B-1) as a [B] acid generator, (C-1) 3.6 as a [C] acid diffusion control agent A radiation-sensitive resin composition (J) is prepared by blending parts by mass, 4280 parts by mass of (E-1) as a solvent and 1830 parts by mass of (E-2), and filtering with a membrane filter with a pore size of 0.2 μm. -31) was prepared.

[Examples 82 to 85 and Comparative Examples 4 to 6]
Radiation-sensitive resin compositions (J-32) to (J-35) and (CJ-4) are operated in the same manner as in Example 81 except that the components of the types and blending amounts shown in Table 5 below are used. ) To (CJ-6) were prepared.

<Formation of resist pattern (3)>
The radiation sensitive resin composition was applied to an 8-inch silicon wafer surface using a spin coater (“CLEAN TRACK ACT 8” from Tokyo Electron Ltd.), and PB was performed at 90 ° C. for 60 seconds. Then, it cooled at 23 degreeC for 30 second, and formed the resist film with an average thickness of 50 nm. Next, the resist film was irradiated with an electron beam using a simple type electron beam lithography system (“HL800D” manufactured by Hitachi, Ltd., output: 50 KeV, current density: 5.0 A / cm ² ). After irradiation, PEB was performed at 120 ° C. for 60 seconds. Thereafter, development was performed at 23.degree. C. for 30 seconds using a 2.38% by weight aqueous solution of TMAH as an alkaline developer, washed with water, and dried to form a positive resist pattern.

<Formation of resist pattern (4)>
A negative resist pattern is operated in the same manner as in the formation of the resist pattern (1) except that the organic solvent is developed using n-butyl acetate instead of the aqueous solution of TMAH and washing with water is not performed. Formed.

<Evaluation>
Evaluation similar to the said Examples 51-80 was implemented about the resist pattern formed using said each radiation sensitive resin composition. The evaluation results are shown in Table 6 below. The radiation sensitive resin composition for electron beam exposure can be evaluated as "good" when the LWR performance is 5.0 nm or less, and "defect" when it exceeds 5.0 nm. Evaluation criteria for the resolution, the rectangularity of the cross-sectional shape, and the depth of focus are the same as in the radiation sensitive resin composition for ArF exposure.

  From the results of Tables 3, 4 and 6, the radiation sensitive resin compositions of the examples have LWR performance and resolution even in the case of ArF exposure and electron beam exposure, and also in the case of alkali development and organic solvent development. It is understood that the rectangularity of the cross-sectional shape, the depth of focus, the MEEF performance, the development defect suppressing property and the film shrinkage suppressing property are excellent. In addition, it is known that electron beam exposure and EUV exposure become the same tendency, and according to the radiation sensitive resin composition of the example, it is presumed that LWR performance etc. is excellent even in the case of EUV exposure. .

  According to the radiation sensitive resin composition and resist pattern forming method of the present invention, LWR is small, resolution is high, and rectangular property of cross-sectional shape is excellent while exhibiting excellent depth of focus, MEEF performance and film shrinkage suppressing property. A resist pattern with few development defects can be formed. The polymer of the present invention can be suitably used as a polymer component of the radiation sensitive resin composition. The compound of the present invention can be suitably used as a monomer of the polymer. Therefore, these can be suitably used for semiconductor device manufacture whose miniaturization is expected to further progress in the future.

Claims (9)

The polymer which has a 1st structural unit containing group represented by following formula (1) or (1 '), and the radiation sensitive resin composition containing a radiation sensitive acid generator.

(In formula (1), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or a carbon in which these groups are combined with each other and these are combined) R ³ represents a ring structure having 3 to 20 ring members, and R ³ is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms, n is an integer of 0 to 13. n is an integer of 0 to 13. In the case of two or more, the plurality of R ^{3 s} may be the same or different, and two of the plurality of R ^{3 s} may be combined with each other to form —CH ₂ —, —CH ₂ —CH ₂ —, —C (CH ₃ ) _And R ⁴ may be a divalent hydrocarbon group having 1 to 20 carbon atoms, and L may be a divalent linking group having a hetero atom. And p and q each independently represent an integer of 1 to 3. * in the first structural unit The site | part couple | bonded with parts other than group represented by said Formula (1) is shown.
In formula (1 ′), E ¹ , E ² and E ³ are each independently an oxygen atom or a sulfur atom. R ^{3 '} is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. n 'is an integer of 0 to 13. 'If is 2 or more, plural R ^3' n may be the same or different, two of the plurality of R ^{3 ',} are combined with each other _{-CH 2 -, - CH 2 -CH} 2 -, - It may form a C (CH ₃ ) ₂ -or -O- crosslink. R ^{4 ′} is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. L ′ is a single bond or a divalent linking group having a hetero atom. p ′ and q ′ are each independently an integer of 1 to 3. * Shows the site | part couple | bonded with parts other than group represented by said Formula (1 ') in said 1st structural unit. ) The radiation sensitive resin composition according to claim 1, wherein the first structural unit is represented by the following formula (1-1), (1-2) or (1-3).

(In the formulas (1-1) to (1-3), Z is a group represented by the above formula (1) or (1 ′).
In formula (1-1), R ⁵ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
In formula (1-2), R ⁶ is a hydrogen atom or a methyl group. R ⁷ is a single bond, -O-, -COO- or -CONH-. R ⁸ is a C 1-10 monovalent organic group. a is an integer of 0 to 4; When a is 2 or more, plural R ^{8 s} may be the same or different.
In formula (1-3), R ⁹ is a hydrogen atom or a methyl group. R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. Two or more of one or more of R ¹⁰ and R ¹¹ and R ¹² may be combined together with the carbon atoms or carbon chains to which they are attached to form a ring structure having 3 to 20 ring members. Good. b is an integer of 1 to 4; When b is 2 or more, plural R ^{10 s} may be the same or different, and plural R ^{11 s} may be the same or different. R ¹³ is a single bond or a divalent organic group having 1 to 20 carbon atoms. R ¹² and R ¹³ may form a ring structure having 3 to 20 ring members, which are configured together with the carbon atoms which are combined with each other and to which they are bonded. ) The radiation sensitive resin composition according to claim 1 or 2, wherein the polymer further has a second structural unit represented by the following formula (2).

(In formula (2), R ¹⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ¹⁵ is a C 1 to C 20 monovalent hydrocarbon group. R ¹⁶ and R ^{And 17} each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a C 3 to 20 alicyclic ring formed together with the carbon atoms to which these groups are combined and bonded to one another. Represents the structure)   The said polymer is structural units other than the said 1st structural unit, Comprising: The lactone structure, a cyclic carbonate structure, a sultone structure, or 3rd structural unit containing these combination is further included. The radiation sensitive resin composition as described in 3. The radiation sensitive resin composition according to any one of claims 1 to 4, wherein the radiation sensitive acid generator is represented by the following formula (3).

(In the formula (3), R ¹⁸ is .R ¹⁹ is a monovalent group containing a monovalent radical or ring members 6 or more aliphatic heterocyclic structure containing ring members 6 or more alicyclic structures, the carbon 1 to 10 fluorinated alkanediyl groups, X ⁺ is a monovalent radiation-sensitive onium cation.) Forming a resist film,
Exposing the resist film; and developing the exposed resist film.
The resist pattern formation method which forms the said resist film by the radiation sensitive resin composition of any one of Claims 1-5. The polymer which has a structural unit containing group represented by following formula (1) or (1 ').

(In formula (1), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or a carbon in which these groups are combined with each other and these are combined) R ³ represents a ring structure having 3 to 20 ring members, and R ³ is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms, n is an integer of 0 to 13. n is an integer of 0 to 13. In the case of two or more, the plurality of R ^{3 s} may be the same or different, and two of the plurality of R ^{3 s} may be combined with each other to form —CH ₂ —, —CH ₂ —CH ₂ —, —C (CH ₃ ) _And R ⁴ may be a divalent hydrocarbon group having 1 to 20 carbon atoms, and L may be a divalent linking group having a hetero atom. And p and q each independently represent an integer of 1 to 3. * in the first structural unit The site | part couple | bonded with parts other than group represented by said Formula (1) is shown.
In formula (1 ′), E ¹ , E ² and E ³ are each independently an oxygen atom or a sulfur atom. R ^{3 '} is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. n 'is an integer of 0 to 13. 'If is 2 or more, plural R ^3' n may be the same or different, two of the plurality of R ^{3 ',} are combined with each other _{-CH 2 -, - CH 2 -CH} 2 -, - It may form a C (CH ₃ ) ₂ -or -O- crosslink. R ^{4 ′} is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. L ′ is a single bond or a divalent linking group having a hetero atom. p ′ and q ′ are each independently an integer of 1 to 3. * Shows the site | part couple | bonded with parts other than group represented by said Formula (1 ') in said 1st structural unit. ) The polymer according to claim 7, wherein the structural unit is represented by the following formula (1-1), (1-2) or (1-3).

(In the formulas (1-1) to (1-3), Z is a group represented by the above formula (1) or (1 ′).
In formula (1-1), R ⁵ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
In formula (1-2), R ⁶ is a hydrogen atom or a methyl group. R ⁷ is a single bond, -O-, -COO- or -CONH-. R ⁸ is a C 1-10 monovalent organic group. a is an integer of 0 to 4; When a is 2 or more, plural R ^{8 s} may be the same or different.
In formula (1-3), R ⁹ is a hydrogen atom or a methyl group. R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. Two or more of one or more of R ¹⁰ and R ¹¹ and R ¹² may be combined together with the carbon atoms or carbon chains to which they are attached to form a ring structure having 3 to 20 ring members. Good. b is an integer of 1 to 4; When b is 2 or more, plural R ^{10 s} may be the same or different, and plural R ^{11 s} may be the same or different. R ¹³ is a single bond or a divalent organic group having 1 to 20 carbon atoms. R ¹² and R ¹³ may form a ring structure having 3 to 20 ring members, which are configured together with the carbon atoms which are combined with each other and to which they are bonded. ) The compound represented by following formula (i-1), (i-2) or (i-3) .

(In the formulas (i-1) to (i-3), Z is a group represented by the following formula (1) or (1 ').
In formula (i-1), R ⁵ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
In formula (i-2), R ⁶ is a hydrogen atom or a methyl group. R ⁷ is a single bond, -O-, -COO- or -CONH-. R ⁸ is a C 1-10 monovalent organic group. a is an integer of 0 to 4; When a is 2 or more, plural R ^{8 s} may be the same or different.
In formula (1-3), R ⁹ is a hydrogen atom or a methyl group. R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. 1 or more of the plurality of R ¹⁰ and R ¹¹ and R ¹² are, may form a ring structure composed of ring members 3 to 20 together with the carbon atom or carbon chain that binds these aligned with one another Good. b is an integer of 1 to 4; When b is 2 or more, plural R ^{10 s} may be the same or different, and plural R ^{11 s} may be the same or different. R ¹³ is a single bond or a divalent organic group having 1 to 20 carbon atoms. R ¹² and R ¹³ may form a ring structure having 3 to 20 ring members, which are configured together with the carbon atoms which are combined with each other and to which they are bonded. )

(In formula (1), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or a carbon in which these groups are combined with each other and these are combined) R ³ represents a ring structure having 3 to 20 ring members, and R ³ is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms, n is an integer of 0 to 13. n is an integer of 0 to 13. In the case of two or more, the plurality of R ^{3 s} may be the same or different, and two of the plurality of R ^{3 s} may be combined with each other to form —CH ₂ —, —CH ₂ —CH ₂ —, —C (CH ₃ ) _And R ⁴ may be a divalent hydrocarbon group having 1 to 20 carbon atoms, and L may be a divalent linking group having a hetero atom. And p and q each independently represent an integer of 1 to 3. * in the first structural unit The site | part couple | bonded with parts other than group represented by said Formula (1) is shown.
In formula (1 ′), E ¹ , E ² and E ³ are each independently an oxygen atom or a sulfur atom. R ^{3 '} is a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms. n 'is an integer of 0 to 13. 'If is 2 or more, plural R ^3' n may be the same or different, two of the plurality of R ^{3 ',} are combined with each other _{-CH 2 -, - CH 2 -CH} 2 -, - It may form a C (CH ₃ ) ₂ -or -O- crosslink. R ^{4 ′} is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. L ′ is a single bond or a divalent linking group having a hetero atom. p ′ and q ′ are each independently an integer of 1 to 3. * Shows the site | part couple | bonded with parts other than group represented by said Formula (1 ') in said 1st structural unit. )