JP6069691B2 - Acid diffusion controller, radiation sensitive resin composition, and resist pattern forming method - Google Patents

Description

  The present invention relates to an acid diffusion controller, a radiation sensitive resin composition, a resist pattern forming method, a compound, and a method for producing the compound.

  The chemically amplified radiation-sensitive resin composition generates an acid from an acid generator at an exposed portion by irradiation with exposure light such as ArF excimer laser light or KrF excimer laser light, and the reaction is carried out by reaction using this acid as a catalyst. The dissolution rate of the part and the unexposed part in the developer is changed to form a resist pattern on the substrate.

  Such radiation-sensitive resin compositions are required to improve various performances such as resolution as processing technology becomes finer. In response to this requirement, an acid diffusion control agent is contained in the radiation sensitive resin composition for the purpose of appropriately controlling the diffusion of the acid generated from the acid generator. As this acid diffusion control agent, a nitrogen atom-containing compound containing an ether group, a hydroxy group or an ester group as a polar group and further having a ring structure is known. According to this acid diffusion control agent, resolution and It is said that the depth of focus can be increased (see JP 2002-363148 A and JP 2002-226470 A).

  Under such circumstances, in the present situation where the miniaturization of the resist pattern is increasingly advanced, it is required to further improve the resolution and the depth of focus, and in addition, the line width of the resist pattern is varied. It is also required to have excellent line width roughness (LWR) performance. Furthermore, in the conventional acid diffusion controller, the formed resist pattern tends to have a top loss or the like, and it is also required to improve the rectangularity of the cross-sectional shape of the resist pattern. However, the above conventional radiation-sensitive resin composition cannot satisfy these requirements.

JP 2002-363148 A JP 2002-226470 A

  The present invention has been made based on the circumstances as described above, and its purpose is to provide an acid diffusion controller excellent in the LWR performance, resolution, rectangularity of the cross-sectional shape and depth of focus of the radiation-sensitive resin composition. It is to provide.

（式（１）中、
Ｒ^１は、炭素数１〜２０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^２若しくはＲ^３と結合して環員数３〜３０の環構造の一部を形成している。
Ｒ^２は、炭素数１〜２０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^１と結合して環員数３〜３０の環構造の一部を形成している。
Ｒ^３は、水素原子、炭素数１〜１０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^１若しくはＲ^４と結合して環員数３〜３０の環構造の一部を形成している。
Ｒ^４は、水素原子、炭素数１〜１０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^３と結合して環員数３〜３０の環構造の一部を形成している。
ｎは、１又は２である。ｎが２の場合、複数のＲ^３及びＲ^４はそれぞれ同一でも異なっていてもよい。
Ｒ^５及びＲ^６は、それぞれ独立して、水素原子、炭素数１〜１０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^５及びＲ^６が互いに結合してこれらが結合している窒素原子と共に環員数３〜３０の環構造を形成している。
Ｒは、水素原子又は炭素数１〜１０の炭化水素基である。
Ｘは、単結合又は炭素数１〜２０の２価の有機基である。
Ｙは、−ＣＯ−又は−ＳＯ_２−である。） The invention made to solve the above problems is
It is an acid diffusion controller comprising a compound represented by the following formula (1).

(In the formula (1),
R ¹ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ² or R ³ to form a part of a ring structure having 3 to 30 ring members .
R ² represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ¹ to form a part of a ring structure having 3 to 30 ring members.
R ³ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O between the carbon and carbon of this group. -, _- or a group containing at least one selected from SO 2 NR-, and the group consisting of -CONR-, or combined with ^{R 1} or ^{R 4} form a part of the ring structure of ring members 3-30 doing.
R ⁴ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O between the carbon and carbon of this group. -, _- or a group containing at least one selected from SO 2 NR-, and the group consisting of -CONR-, or combined with ^{R 3} to form a part of the ring structure of ring members 3-30 .
n is 1 or 2. When n is 2, the plurality of R ³ and R ⁴ may be the same or different.
R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or -O-, -CO-, -COO-,- A group containing at least one selected from the group consisting of SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—, or R ⁵ and R ⁶ are bonded to each other. A ring structure having 3 to 30 ring members is formed together with the nitrogen atom.
R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
X is a single bond or a divalent organic group having 1 to 20 carbon atoms.
Y is —CO— or —SO ₂ —. )

The radiation sensitive resin composition of the present invention is
[A] a polymer having an acid dissociable group,
[B] an acid generator, and [C] the acid diffusion controller.

The resist pattern forming method of the present invention comprises:
(1) A step of forming a resist film using the radiation-sensitive resin composition,
(2) a step of exposing the resist film; and (3) a step of developing the exposed resist film.

（式（１）中、
Ｒ^１は、炭素数１〜２０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^２若しくはＲ^３と結合して環員数３〜３０の環構造の一部を形成している。
Ｒ^２は、炭素数１〜２０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^１と結合して環員数３〜３０の環構造の一部を形成している。
Ｒ^３は、水素原子、炭素数１〜１０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^１若しくはＲ^４と結合して環員数３〜３０の環構造の一部を形成している。
Ｒ^４は、水素原子、炭素数１〜１０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^３と結合して環員数３〜３０の環構造の一部を形成している。
ｎは、１又は２である。ｎが２の場合、複数のＲ^３及びＲ^４はそれぞれ同一でも異なっていてもよい。
Ｒ^５及びＲ^６は、それぞれ独立して、水素原子、炭素数１〜１０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^５及びＲ^６が互いに結合してこれらが結合している窒素原子と共に環員数３〜３０の環構造を形成している。
Ｒは、水素原子又は炭素数１〜１０の炭化水素基である。
Ｘは、単結合又は炭素数１〜２０の２価の有機基である。
Ｙは、−ＣＯ−又は−ＳＯ_２−である。） The compound of the present invention is represented by the following formula (1).

(In the formula (1),
R ¹ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ² or R ³ to form a part of a ring structure having 3 to 30 ring members .
R ² represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ¹ to form a part of a ring structure having 3 to 30 ring members.
R ³ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O between the carbon and carbon of this group. -, _- or a group containing at least one selected from SO 2 NR-, and the group consisting of -CONR-, or combined with ^{R 1} or ^{R 4} form a part of the ring structure of ring members 3-30 doing.
R ⁴ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O between the carbon and carbon of this group. -, _- or a group containing at least one selected from SO 2 NR-, and the group consisting of -CONR-, or combined with ^{R 3} to form a part of the ring structure of ring members 3-30 .
n is 1 or 2. When n is 2, the plurality of R ³ and R ⁴ may be the same or different.
R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or -O-, -CO-, -COO-,- A group containing at least one selected from the group consisting of SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—, or R ⁵ and R ⁶ are bonded to each other. A ring structure having 3 to 30 ring members is formed together with the nitrogen atom.
R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
X is a single bond or a divalent organic group having 1 to 20 carbon atoms.
Y is —CO— or —SO ₂ —. )

（式（ｉ−ａ）、式（ｉ−ｂ）及び式（１’）中、
Ｒ^１は、炭素数１〜２０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^２と結合して環員数３〜３０の環構造の一部を形成している。
Ｒ^２は、炭素数１〜２０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^１と結合して環員数３〜３０の環構造の一部を形成している。
Ｒ^３ａ、Ｒ^３ｂ及びＲ^４ｂは、それぞれ独立して、水素原子、炭素数１〜１０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基である。
Ｒ^５及びＲ^６は、それぞれ独立して、水素原子、炭素数１〜１０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^５及びＲ^６が互いに結合してこれらが結合している窒素原子と共に環員数３〜３０の環構造を形成している。
Ｒは、水素原子又は炭素数１〜１０の炭化水素基である。
Ｙは、−ＣＯ−又は−ＳＯ_２−である。） The method for producing the compound of the present invention comprises:
It is a manufacturing method of the compound represented by following formula (1 ') which has a process with which the compound represented by following formula (ia) and the compound represented by following formula (ib) are made to react.

(In the formula (ia), the formula (ib) and the formula (1 ′),
R ¹ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ² to form a part of a ring structure having 3 to 30 ring members.
R ² represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ¹ to form a part of a ring structure having 3 to 30 ring members.
R ^3a , R ^3b, and R ^4b are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO between the carbon and carbon of this group. It is a group containing at least one selected from the group consisting of —, —SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—.
R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or -O-, -CO-, -COO-,- A group containing at least one selected from the group consisting of SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—, or R ⁵ and R ⁶ are bonded to each other. A ring structure having 3 to 30 ring members is formed together with the nitrogen atom.
R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Y is —CO— or —SO ₂ —. )

（式（ｉ−ａ’）、式（ｉ−ｂ）及び式（２’）中、
Ｒ^２は、炭素数１〜２０の１価の炭化水素基、又はこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基である。
Ｒ^４ａ及びＲ^４ｂは、それぞれ独立して、水素原子、炭素数１〜１０の１価の炭化水素基、又はこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基である。
Ｒ^７は、（ｋ＋２）価の炭化水素基である。
ｋは、０〜６の整数である。
ｐは、０又は１である。
Ｒ^８は、炭素数１〜２０の１価の炭化水素基、又はこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基である。
ｋが２以上の場合、複数のＲ^８は同一でも異なっていてもよい。
Ｒ^５及びＲ^６は、それぞれ独立して、水素原子、炭素数１〜１０の１価の炭化水素基、若しくはこの基の炭素−炭素間に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＳＯ_２−、−ＳＯ_２Ｏ−、−ＳＯ_２ＮＲ−及び−ＣＯＮＲ−からなる群より選ばれる少なくとも１種を含む基であるか、又はＲ^５及びＲ^６が互いに結合してこれらが結合している窒素原子と共に環構造を形成している。
Ｒは、水素原子又は炭素数１〜１０の炭化水素基である。
Ｙは、−ＣＯ−又は−ＳＯ_２−である。
Ｚは、−ＣＯ−又は−ＳＯ_２−である。
ｍは、０又は１である。） The method for producing another compound of the present invention includes:
It is a method for producing a compound represented by the following formula (2 ′) having a step of reacting a compound represented by the following formula (ia ′) with a compound represented by the following formula (ib). .

(In the formula (ia ′), the formula (ib) and the formula (2 ′),
R ² is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—.
R ^4a and R ^4b each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO—, — It is a group containing at least one selected from the group consisting of SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—.
R ⁷ is a (k + 2) -valent hydrocarbon group.
k is an integer of 0-6.
p is 0 or 1.
R ⁸ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—.
When k is 2 or more, the plurality of R ⁸ may be the same or different.
R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or -O-, -CO-, -COO-,- A group containing at least one selected from the group consisting of SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—, or R ⁵ and R ⁶ are bonded to each other. It forms a ring structure with the nitrogen atom.
R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Y is —CO— or —SO ₂ —.
Z is —CO— or —SO ₂ —.
m is 0 or 1. )

  Here, the “hydrocarbon group” refers to a group composed of a carbon atom and a hydrogen atom, and includes “chain hydrocarbon group”, “alicyclic hydrocarbon group” and “aromatic hydrocarbon group”. being classified. The “chain hydrocarbon group” refers to a hydrocarbon group that does not include a cyclic structure and is composed only of a chain structure. The “alicyclic hydrocarbon group” refers to a hydrocarbon group containing only an alicyclic structure as a ring structure. However, it is not necessary to be composed only of the alicyclic structure, and a part thereof may include a chain structure. “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 only of an aromatic ring structure, and a part thereof may include an alicyclic structure or a chain structure.

  According to the acid diffusion controller of the present invention, a radiation sensitive resin composition containing the acid diffusion control agent, and a resist pattern forming method using the radiation sensitive resin composition, the LWR is small and the resolution is high while exhibiting a wide depth of focus. And a resist pattern that is excellent in the rectangular shape of the cross-sectional shape can be formed. The compound of the present invention can be suitably used as the acid diffusion controller. Moreover, according to the manufacturing method of the compound of this invention, the said compound can be manufactured simply and with a sufficient yield. Therefore, they can be suitably used for pattern formation in semiconductor device manufacturing, which is expected to become increasingly finer in the future.

<Acid diffusion control agent>
The acid diffusion controller (hereinafter also referred to as “acid diffusion controller (I)”) is composed of a compound represented by the above formula (1) (hereinafter also referred to as “compound (I)”). Since the acid diffusion controller (I) is composed of the compound (I), the radiation-sensitive resin composition containing the compound is excellent in LWR performance, resolution, rectangularity of the cross-sectional shape, and depth of focus. The acid diffusion controller (I) may contain one or more compounds (I). The reason why the above effect is achieved when the acid diffusion controller (I) is composed of the compound (I) is not necessarily clear, but can be inferred as follows, for example.
Compound (I) has two nitrogen atoms separated by a suitable distance, one of which can interact strongly with the acid and the other one is adjacent to —SO _2. A sulfonamide group or a carboxylic acid amide group is formed together with-or -CO-, and this group can moderately interact with the polymer contained in the radiation-sensitive resin composition. Since the compound (I) has such a specific structure, the compound (I) has higher affinity with a polymer or the like constituting the resist film than the conventional nitrogen atom-containing compound. Is unevenly distributed. Further, diffusion of compound (I) in the resist film is moderately suppressed, and sublimation from the resist film is reduced. As a result, the radiation sensitive resin composition containing the compound (I) is excellent in LWR performance, resolution, rectangularity of the cross-sectional shape, and depth of focus.

<Compound (I)>
Compound (I) is represented by the following formula (1).

In the above formula (1),
R ¹ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ² or R ³ to form a part of a ring structure having 3 to 30 ring members .
R ² represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ¹ to form a part of a ring structure having 3 to 30 ring members.
R ³ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O between the carbon and carbon of this group. -, _- or a group containing at least one selected from SO 2 NR-, and the group consisting of -CONR-, or combined with ^{R 1} or ^{R 4} form a part of the ring structure of ring members 3-30 doing.
R ⁴ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O between the carbon and carbon of this group. -, _- or a group containing at least one selected from SO 2 NR-, and the group consisting of -CONR-, or combined with ^{R 3} to form a part of the ring structure of ring members 3-30 .
n is 1 or 2. When n is 2, the plurality of R ³ and R ⁴ may be the same or different.
R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or -O-, -CO-, -COO-,- A group containing at least one selected from the group consisting of SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—, or R ⁵ and R ⁶ are bonded to each other. A ring structure having 3 to 30 ring members is formed together with the nitrogen atom.
R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
X is a single bond or a divalent organic group having 1 to 20 carbon atoms.
Y is —CO— or —SO ₂ —.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² include a chain hydrocarbon group having 1 to 20 carbon atoms and an alicyclic hydrocarbon having 3 to 20 carbon atoms. Group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like.

Examples of the chain hydrocarbon group include:
Alkyl groups such as methyl, ethyl, propyl and butyl groups;
An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group;
Examples thereof include alkynyl groups such as ethynyl group, propynyl group, and butynyl group.
Among these, an alkyl group is preferable, and a methyl group and an ethyl group are more preferable.

Examples of the alicyclic hydrocarbon group include:
A monocyclic cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-i-propylcyclopentan-1-yl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group;
A polycyclic cycloalkyl group such as a norbornyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group, a 2-methyladamantan-2-yl group, a 2-i-propyladamantan-2-yl group;
A monocyclic cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group;
Examples thereof include polycyclic cycloalkenyl groups such as norbornenyl group and tricyclodecenyl group.
Among these, a cycloalkyl group is preferable, a monocyclic cycloalkyl group is more preferable, and a cyclohexyl group is more preferable.

Examples of the aromatic hydrocarbon group include:
Aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, methylanthryl;
Examples thereof include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group and naphthylmethyl group.
Among these, an aryl group is preferable and a phenyl group is more preferable.

Examples of the group containing —O— between the carbon and carbon of the hydrocarbon group represented by R ¹ and R ² include R ^α —O—R ^β —, R ^α —O—R ^β —O—. R ^γ- and the like can be mentioned. R ^α is a monovalent hydrocarbon group having 1 to 20 carbon atoms. ^Rβ and ^Rγ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms. R ^α and R ^β , R ^β and R ^γ and / or R ^α and R ^γ may be bonded to each other to form a ring structure.
In particular,
A hydrocarbon group substituted with an oxyhydrocarbon group such as a methoxymethyl group, a methoxyethyl group, a cyclohexyloxymethyl group, an ethoxycyclohexyl group, a phenoxyphenyl group, a phenoxybenzyl group, or a naphthyloxymethyl group;
A group having a cyclic acetal ring (including a cyclic ketal ring) such as a 1,3-dioxa-2,2-dimethylcyclopentan-4-ylmethyl group and a 1,3-dioxacyclopentan-4-ylmethyl group;
7- (1,3-Dioxa-2,2-dimethylcyclopentan-4-yl) -3,3-dimethyl-2,4,8-trioxabicyclo [3,3,0] octane-6-yl group , 7- (1,3-dioxa-spiro [adamantane-2,2 ′] cyclopentan-4-yl) -spiro [adamantane-3,3 ′]-2,4,8-trioxabicyclo [3,3 , 0] octane-6-yl group and the like, and groups having an oxacycloalkane structure and a cyclic acetal ring.

Examples of the group containing —COO— between carbon and carbon of the hydrocarbon group represented by R ¹ and R ² include R ^α -COO-R ^β- , R ^α -OCO-R ^β- , R ^α- COO-R ^β- COO-R ^γ- , R ^α -COO-R ^β -OCO-R ^γ- , R ^α -OCO-R ^β -OCO-R ^γ- , R ^α -OCO-R ^β -COO -R γ ^-, and the like. R ^α is a monovalent hydrocarbon group having 1 to 20 carbon atoms. ^Rβ and ^Rγ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms. R ^α and R ^β , R ^β and R ^γ and / or R ^α and R ^γ may be bonded to each other to form a ring structure.
In particular,
Oxycarbonyl hydrocarbon group or carbonyloxy hydrocarbon such as methoxycarbonylmethyl group, methylcarbonyloxymethyl group, cyclohexylcarbonyloxymethyl group, ethoxycarbonylcyclohexyl group, phenoxycarbonylphenyl group, phenylcarbonyloxybenzyl group, naphthyloxycarbonylmethyl group A hydrocarbon group substituted with a group;
Lactones such as butyrolactone-yl group, valerolactone-yl group, caprolactone-yl group, norbornanelactone-yl group, 5-oxo-4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-yl group A group having a structure;
Examples include ester group-containing chain groups having a group containing a lactone structure such as a lactone-yloxycarbonylalkyl group such as a norbornanelactone-yloxycarbonylmethyl group and a butyrolactone-yloxycarbonylmethyl group.

Examples of the group containing —SO ₂ O— between carbon and carbon of the hydrocarbon group represented by R ¹ and R ² include R ^α —SO ₂ O—R ^β — and R ^α —OSO ₂ —. _{^{R β -, R α -SO 2}} O-R β -SO 2 O-R γ -, R α -SO 2 O-R β -OSO 2 -R γ -, R α -OSO 2 -R β -OSO 2 _{^{-R γ -, R α -OSO 2}} -R β -SO 2 O-R γ - , and the like. R ^α is a monovalent hydrocarbon group having 1 to 20 carbon atoms. ^Rβ and ^Rγ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms. R ^α and R ^β , R ^β and R ^γ and / or R ^α and R ^γ may be bonded to each other to form a ring structure.
In particular,
Oxysulfonyl hydrocarbon group or sulfonyloxy hydrocarbon such as methoxysulfonylmethyl group, methylsulfonyloxymethyl group, cyclohexylsulfonyloxymethyl group, ethoxysulfonylcyclohexyl group, phenoxysulfonylphenyl group, phenylsulfonyloxybenzyl group, naphthyloxysulfonylmethyl group A hydrocarbon group substituted with a group;
And groups having a sultone structure such as a butyrosulton-yl group, a valerosulton-yl group, and a norbornane sultone-yl group.

Examples of the group containing —SO ₂ NR— between carbon and carbon of the hydrocarbon group represented by R ¹ and R ² include R ^α —SO ₂ NR—R ^β —, R ^α —NRSO ₂ —. _{^{R β -, R α -SO 2}} NR-R β -SO 2 NR-R γ -, R α -SO 2 NR-R β -NRSO 2 -R γ -, R α -NRSO 2 -R β -NRSO 2 _{^{-R γ -, R α -NRSO 2}} -R β -SO 2 NR-R γ - , and the like. R ^α is a monovalent hydrocarbon group having 1 to 20 carbon atoms. ^Rβ and ^Rγ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms. R is a C1-C10 hydrocarbon group. R ^α and R ^β , R ^β and R ^γ and / or R ^α and R ^γ may be bonded to each other to form a ring structure.
In particular,
Methylaminosulfonylmethyl group, methylsulfonylaminomethyl group, cyclohexylsulfonylaminomethyl group, ethylaminosulfonylcyclohexyl group, phenylaminosulfonylphenyl group, phenylsulfonylaminobenzyl group, aminosulfonyl hydrocarbon group or sulfonylamino group of naphthylaminosulfonylmethyl group A hydrocarbon group substituted by a hydrocarbon group;
Examples thereof include groups having a sultam structure such as a propane sultam-yl group, a butane sultam-yl group, and a norbornane sultam-yl group.

Examples of the group containing —CONR— between carbon and carbon of the hydrocarbon group represented by R ¹ and R ² include R ^α -CONR-R ^β- , R ^α -NRCO-R ^β- , R ^α- CONR-R ^β- CONR-R ^γ- , R ^α -CONR-R ^β -NRCO-R ^γ- , R ^α -NRCO-R ^β -NRCO-R ^γ- , R ^α -NRCO-R ^β -CONR -R γ ^-, and the like. R ^α is a monovalent hydrocarbon group having 1 to 20 carbon atoms. ^Rβ and ^Rγ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms. R is a C1-C10 hydrocarbon group. R ^α and R ^β , R ^β and R ^γ and / or R ^α and R ^γ may be bonded to each other to form a ring structure.
In particular,
Aminocarbonyl hydrocarbon group or carbonyl such as methylaminocarbonylmethyl group, methylcarbonylaminomethyl group, cyclohexylcarbonylaminomethyl group, ethylaminocarbonylcyclohexyl group, phenylaminocarbonylphenyl group, phenylcarbonylaminobenzyl group, naphthylaminocarbonylmethyl group A hydrocarbon group substituted with an amino hydrocarbon group;
Examples thereof include groups having a lactam structure such as a butyrolactam-yl group, a valerolactam-yl group, a caprolactam-yl group, and a norbornane lactam-yl group.

Examples of the ring structure formed together with the nitrogen atom in which R ¹ is partly bonded to R ² and these are bonded include:
Monocyclic azacycloalkane structures such as an azacyclopropane structure, an azacyclobutane structure, an azacyclopentane structure (pyrrolidine structure), an azacyclohexane structure (piperidine structure), an azacycloheptane structure, an azacyclooctane structure, an azacyclodecane structure;
A polycyclic azacycloalkane structure such as an azabicyclo [2.2.1] heptane structure, an azabicyclo [2.2.2] octane structure, an azatricyclo [3.3.1.1 ^3,7 ] decane structure;
And azaoxacycloalkane structures such as an azaoxacyclopropane structure and an azaoxacyclohexane structure (including a morpholine structure).
Among these, monocyclic azacycloalkane structure and azaoxacycloalkane structure are preferable, azacyclopentane structure, azacyclohexane structure and azaoxacyclohexane structure are more preferable, azacyclohexane structure and 1,4-azaoxacyclohexane structure (A morpholine structure) is more preferable, and a 1,4-azaoxacyclohexane structure is particularly preferable.

Examples of the ring structure having 3 to 30 ring members formed together with the nitrogen atom to which R ¹ is a part and bonded to R ³ , the carbon atom to which R ¹ is bonded, the carbon atom to which R ³ is bonded, and Y include: , Lactam ring structure, sultam ring structure, imide ring structure, sulfonimide ring structure and the like. The number of ring members of the ring structure formed together with the nitrogen atom to which R ¹ is a part and bonded to R ³ to which R ¹ is bonded, the carbon atom to which R ³ is bonded, and Y is preferably 5 to 30 5 to 20 is more preferable.
Among these, a lactam ring structure, a sultam ring structure, and an imide ring structure are preferable.

R ¹ is preferably an alkyl group or R ¹ is bonded to R ³ to form a ring structure, and R ¹ is bonded to R ³ to form a ring structure. More preferably, R ¹ is bonded to R ³ to form a lactam ring structure, a sultam ring structure or an imide ring structure, and R ¹ is bonded to R ³ to form a lactam ring having 5 to 20 ring members. It is particularly preferable that a structure, a sultam ring structure having 5 to 20 ring members or an imide ring structure having 5 to 20 ring members is formed, and R ¹ is bonded to R ³ to form a 5-membered lactam ring structure or a 5-membered ring. It is more particularly preferable that a sultam ring structure or a five-membered ring imide structure is formed.

R ² is preferably a hydrocarbon group, R ² is preferably bonded to R ¹ to form a ring structure, and is an alicyclic hydrocarbon group or an aromatic hydrocarbon group, or it is more preferred that R ² form a aza-oxa cycloalkane structure bonded to ring members 5 to 20 and R ^1, a cycloalkyl group or an aryl group, or R ² is bonded to R ¹ More preferably, an azaoxacyclohexane structure is formed, which is a cyclohexyl group or a phenyl group, or R ² is bonded to R ¹ to form a 1,4-azaoxacyclohexane structure (morpholine structure). It is particularly preferred.

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ and R ⁴ include those having 1 to 10 carbon atoms among the hydrocarbon groups exemplified as R ¹ and R ² above. Can be mentioned.

At least selected from the group consisting of —O—, —COO—, —SO ₂ O—, —SO ₂ NR— and —CONR— between the carbon and carbon of the hydrocarbon group represented by R ³ and R ^4. As group containing 1 type, the group etc. which contain C1-C10 as a hydrocarbon group among the same groups illustrated as said R < ¹ > and R < ² >, etc. are mentioned, for example.

Examples of the ring structure having 3 to 30 ring members formed together with the carbon atom to which R ³ is partly bonded and bonded to R ⁴ include, for example,
Cycloalkane structures such as cyclopropane structure, cyclobutane structure, cyclopentane structure, cyclohexane structure, norbornane structure, adamantane structure;
Examples thereof include oxacycloalkane structures such as an oxacyclobutane structure, an oxacyclopentane structure, an oxacyclohexane structure, an oxanorbornane structure, and an oxaadamantane structure. The number of ring members of the ring structure formed together with the carbon atom to which R ³ is partly bonded and bonded to R ⁴ is preferably 5 to 30, and more preferably 5 to 20.

As the R ^3, or an alkyl group, or R ³ is a nitrogen atom to which R ¹ bound to R ¹ is attached, the ring members 3 to 30 together with a carbon atom and Y R ³ is attached It preferably forms a ring structure and is an alkyl group having 1 to 4 carbon atoms, or R ³ is bonded to R ¹ to form an imide ring structure having 5 to 20 ring members, or a lactam having 5 to 20 ring members. It is more preferable to form a ring structure or a sultam ring structure having 5 to 20 ring members, which is a methyl group, or R ³ is bonded to R ¹ to form a 5-membered imide ring structure, More preferably, a lactam ring structure or a 5-membered sultam ring structure is formed.

R ⁴ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

  As said n, 1 is preferable.

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ⁵ and R ⁶ include groups similar to those exemplified as R ³ and R ⁴ .

At least selected from the group consisting of —O—, —COO—, —SO ₂ O—, —SO ₂ NR— and —CONR— between the carbon and carbon of the hydrocarbon group represented by R ⁵ and R ^6. the group containing one, for example, such as the same groups as those exemplified as the R ³ and R ⁴ can be mentioned.

Examples of the ring structure having 3 to 30 ring members formed together with the nitrogen atom to which R ⁵ and R ⁶ are bonded to each other include the same ring structure formed by R ¹ and R ² above. Etc. The number of ring members of the ring structure formed by R ⁵ and R ⁶ bonded together and the nitrogen atom to which they are bonded is preferably 5-30, more preferably 5-20.

R ⁵ and R ⁶ are preferably an alkyl group, or R ⁵ and R ⁶ are bonded to each other to form a ring structure together with the nitrogen atom to which these are bonded. whether it is to 4 alkyl groups, or is more ^{preferably R 5} and the ^{R 6} form a 1,4-aza-cyclohexane structure (piperidine structure), or an ethyl group, or ^{R 5} and ^{R 6} And more preferably form an N-piperidyl group or an N-decahydroquinolinyl group.

  Examples of the divalent organic group having 1 to 20 carbon atoms represented by X include, for example, a hydrocarbon group having 1 to 20 carbon atoms and a part or all of the hydrogen atoms of the hydrocarbon group substituted with a substituent. And a substituted hydrocarbon group, a divalent group having a group containing a hetero atom between carbon and carbon of the substituted hydrocarbon group, and the substituted hydrocarbon group.

The hydrocarbon group having 1 to 20 carbon atoms include, like same groups as those exemplified as R ¹ above and R ² can be mentioned.

  Examples of the substituent include a hydroxy group, a carboxy group, an amino group, a cyano group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; a formyl group and an acetyl group Groups, acyl groups such as propionyl groups; acyloxy groups such as acetoxy groups and propionyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups.

  Examples of the group containing a hetero atom which may be contained between carbon and carbon include one selected from the group consisting of —O—, —S—, —NR′—, —CO— and —CS—. Or the group etc. which combined 2 or more types are mentioned. R ′ is a hydrocarbon group having 1 to 10 carbon atoms.

  X is preferably a single bond or a divalent hydrocarbon group, preferably a single bond or an alkanediyl group, more preferably a single bond or a methanediyl group.

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R in —SO ₂ NR— and —CONR— of R ^{1 to} R ⁶ include the hydrocarbon groups exemplified as R ¹ and R ² above. Examples thereof include those having 1 to 10 carbon atoms.

Preferable examples of compound (I) include a compound represented by the following formula (2) (hereinafter also referred to as “compound (2)”). In the compound (2), in the compound (1), n is 2, R ¹ is bonded to R ³ bonded to the carbon atom adjacent to X, and — (Z) _m —R ⁷ (—R ⁸ ) _k- , having a structure in which a ring structure is formed with a carbon atom adjacent to X, a carbon atom adjacent to Y, and a nitrogen atom to which Y and R ² are bonded. Compound (2) is a cyclic compound containing a nitrogen atom and an unsaturated bond, such as a maleimide compound, a didehydrolactam (α, β-unsaturated lactam) compound, a didehydrosultam (α, β-unsaturated sultam) compound Can be synthesized.

In the above formula (2),
R ² is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—.
R ^3a , R ^4a and R ^4b each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, — _{COO -, - SO 2 -,} - SO 2 O -, - is a group containing at least one SO selected from 2 NR- the group consisting of -CONR-.
R ⁷ is a (k + 2) -valent hydrocarbon group.
k is an integer of 0-6.
p is 0 or 1.
R ⁸ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—.
When k is 2 or more, the plurality of R ⁸ may be the same or different.
R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Z is —CO— or —SO ₂ —.
m is 0 or 1.
R ⁵ , R ⁶ , X and Y are as defined in the above formula (1).

The above monovalent hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 2,} and the carbon of the group - -O between carbon _{-, - COO -, - SO} 2 O -, - SO 2 NR- , and - Examples of the group containing at least one selected from the group consisting of CONR- include the same groups as those exemplified as R ² in the above formula (1).

The monovalent hydrocarbon group having 1 to 10 carbon atoms represented by the above R ^3a , R ^4a and R ^4b , and —O—, —COO—, —SO ₂ O—, — between the carbon and carbon of this group Examples of the group containing at least one selected from the group consisting of SO ₂ NR— and —CONR— include the same groups as those exemplified as R ⁴ in the above formula (1).

Examples of the (k + 2) -valent hydrocarbon group represented by R ⁷ include (k + 1) from the monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified as R ¹ and R ² in the above formula (1). And a group excluding individual hydrogen atoms.

  k is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0.

R ⁷ is preferably a (k + 2) -valent chain hydrocarbon group, more preferably a (k + 2) -valent chain saturated hydrocarbon group, still more preferably an alkanediyl group, and particularly preferably a methanediyl group.

  p is preferably 0 from the viewpoint of the ease of synthesis of compound (2) and the availability of raw materials.

The monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸ above, and —O—, —COO—, —SO ₂ O—, —SO ₂ NR— and — between the carbon and carbon of this group. Examples of the group containing at least one selected from the group consisting of CONR- include the same groups as those exemplified as R ¹ in the above formula (1).

  Examples of the compound (I) include compounds represented by the following formulas (i-1) to (i-18) (hereinafter also referred to as “compounds (i-1) to (i-18)”). It is done.

  Among these, as the compound (I), compounds (i-1) to (i-7) are preferable.

The compound (I) includes the following compound (1 ′) when n is 2, X is a single bond, and R ¹ and R ³ do not form a ring structure in the above formula (1), and the above formula In the case of (2) where X is a single bond and R ^3a bonded to the carbon atom adjacent to Y is a hydrogen atom, the following compound (2 ′) is synthesized, for example, according to the following reaction scheme: Can do. By the above method, compound (I) can be synthesized simply and with good yield. Other compounds (I) can also be synthesized using a known method.

In the above formula (ia), formula (ib) and formula (1 ′),
R ¹ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ² to form a part of a ring structure having 3 to 30 ring members.
R ² represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—, or is bonded to R ¹ to form a part of a ring structure having 3 to 30 ring members.
R ^3a , R ^3b, and R ^4b are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO between the carbon and carbon of this group. It is a group containing at least one selected from the group consisting of —, —SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—.
R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or -O-, -CO-, -COO-,- A group containing at least one selected from the group consisting of SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—, or R ⁵ and R ⁶ are bonded to each other. A ring structure having 3 to 30 ring members is formed together with the nitrogen atom.
R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Y is —CO— or —SO ₂ —. )

In the above formula (ia ′), formula (ib) and formula (2 ′),
R ² is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—.
R ^4a and R ^4b each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or —O—, —CO—, —COO—, — It is a group containing at least one selected from the group consisting of SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—.
R ⁷ is a (k + 2) -valent hydrocarbon group.
k is an integer of 0-6.
p is 0 or 1.
R ⁸ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —O—, —CO—, —COO—, —SO ₂ —, —SO ₂ O—, — It is a group containing at least one selected from the group consisting of SO ₂ NR— and —CONR—.
When k is 2 or more, the plurality of R ⁸ may be the same or different.
R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or -O-, -CO-, -COO-,- A group containing at least one selected from the group consisting of SO ₂ —, —SO ₂ O—, —SO ₂ NR— and —CONR—, or R ⁵ and R ⁶ are bonded to each other. It forms a ring structure with the nitrogen atom.
R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Y is —CO— or —SO ₂ —.
Z is —CO— or —SO ₂ —.
m is 0 or 1.

By reacting the acrylamide compound or vinylsulfonamide compound represented by the above formula (ia) with the amine compound represented by the above (ib) in a solvent such as toluene, the above formula (1) A compound represented by ') is obtained.
A cyclic compound containing a carbon-carbon double bond represented by the above formula (ia ′) and —CO— or —SO ₂ —; an amine compound represented by the above formula (ib); Is reacted in a solvent such as toluene to obtain a compound represented by the above formula (2 ′).

<Radiation sensitive resin composition>
The radiation-sensitive resin composition includes [A] a polymer having an acid dissociable group (hereinafter, also referred to as “[A] polymer”), [B] an acid generator, and [C] the acid diffusion controller ( Hereinafter, it is also referred to as “[C] acid diffusion controller”. In addition to these components, the radiation-sensitive resin composition has a suitable component as an acid diffusion control agent [D] [C] acid diffusion control agent (hereinafter referred to as “[D] other acid diffusion control agent”). And [E] a fluorine atom-containing polymer and a [F] solvent may be further contained, and other optional components may be contained within a range not impairing the effects of the present invention. Hereinafter, each component will be described.

<[A] polymer>
[A] The polymer is a polymer having an acid dissociable group. [A] The polymer is at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure, in addition to a structural unit containing an acid dissociable group (hereinafter also referred to as “structural unit (I)”). It is preferable to further include a structural unit (II) containing a polar group and / or a structural unit (III) having a polar group, and may further include other structural units other than these structural units. [A] The polymer may have one or more of each structural unit. Hereinafter, each structural unit will be described.

[Structural unit (I)]
The structural unit (I) is a structural unit containing an acid dissociable group. The “acid-dissociable group” refers to a group that substitutes a hydrogen atom of an acidic group such as a carboxy group or a hydroxy group and dissociates by the action of an acid.

  Examples of the structural unit (I) include a structural unit (I-1) represented by the following formula (3).

In said formula (3), ^RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R ^p is a monovalent acid dissociable group represented by the above formula (p).
In said formula (p), R ^<p1> , R ^<p2> and R ^<p3> are respectively independently a C1-C4 alkyl group or a C4-C20 cycloalkyl group. However, R ^p2 and R ^p3 may be bonded to each other to form a cycloalkanediyl group having 4 to 20 carbon atoms together with the carbon atom to which they are bonded.

  As the structural unit (I-1), structural units represented by the following formulas (3-1) to (3-4) are preferable.

In the above formulas (3-1) to (3-4), R ^A , R ^p1 , R ^p2 and R ^p3 have the same ^{meaning as} in the above formula (3). i and j are each independently an integer of 1 to 4.

  Examples of the structural unit represented by the above formula (3) and the above formulas (3-1) to (3-4) include a structural unit represented by the following formula.

In the above formula, R ^A has the same meaning as in the above formula (3).

  The structural unit (I) is preferably a structural unit represented by the above formula (3-1) or a structural unit represented by the formula (3-2), and is derived from 1-alkyl-1-cyclopentyl (meth) acrylate. The structural unit derived from 2-alkyl-2-adamantyl (meth) acrylate is more preferred, the structural unit derived from 1-ethyl-1-cyclopentyl (meth) acrylate, 2-ethyl-2-adamantyl (meta More preferred are structural units derived from acrylates.

  As a content rate of structural unit (I), 10 mol%-100 mol% are preferable with respect to all the structural units which comprise a [A] polymer, 20 mol%-80 mol% are more preferable, 30 mol% More preferred is ˜70 mol%. By making the content rate of structural unit (I) into the said range, the LWR performance of the said radiation sensitive resin composition, resolution, the rectangularity of a cross-sectional shape, and a depth of focus can be improved. When the content rate of structural unit (I) is less than the said minimum, the pattern formation property of the said radiation sensitive resin composition may fall.

[Structural unit (II)]
The structural unit (II) is a structural unit containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure. [A] The polymer further has the structural unit (II), whereby the solubility in the developer can be adjusted. Moreover, the adhesiveness of the resist pattern formed from the said radiation sensitive resin composition and a board | substrate can be improved.

  Examples of the structural unit (II) include a structural unit represented by the following formula.

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

  Among these, as the structural unit (II), a structural unit containing a lactone structure and a structural unit containing a sultone structure are preferred, a structural unit containing a lactone structure is more preferred, and a structural unit containing a norbornane lactone structure is more preferred, A structural unit derived from norbornanelactone-yl (meth) acrylate is particularly preferred.

  As a content rate of structural unit (II), 0 mol%-80 mol% are preferable with respect to all the structural units which comprise a [A] polymer, 20 mol%-80 mol% are more preferable, 30 mol% More preferred is ˜70 mol%. By making the content rate of structural unit (II) into the said range, the solubility to the developing solution of a [A] polymer can be made more moderate. Moreover, the adhesiveness of the resist pattern formed from the said radiation sensitive resin composition and a board | substrate can be improved more. When the content rate of structural unit (II) exceeds the said upper limit, the pattern formation property of the said radiation sensitive resin composition may fall.

[Structural unit (III)]
The structural unit (III) is a structural unit having a polar group (except for those corresponding to the structural unit (II)). [A] The polymer further has the structural unit (III), whereby the solubility in the developer can be adjusted.

  Examples of the polar group include a hydroxy group, a carboxy group, a cyano group, a nitro group, and a sulfonamide group. Among these, a hydroxy group and a carboxy group are preferable, and a hydroxy group is more preferable.

  Examples of the structural unit (III) include a structural unit represented by the following formula.

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

  As a content rate of structural unit (III), 0 mol%-80 mol% are preferable with respect to all the structural units which comprise a [A] polymer, 20 mol%-75 mol% are more preferable, 40 mol% More preferred is ˜70 mol%. By making the content rate of structural unit (III) into the said range, the solubility to the developing solution of a [A] polymer can be made more moderate. When the content rate of structural unit (III) exceeds the said upper limit, the pattern formation property of the said radiation sensitive resin composition may fall.

[Other structural units]
[A] The polymer may have other structural units other than the structural units (I) to (III). Examples of the other structural units include structural units having a non-dissociable alicyclic hydrocarbon group. As a content rate of the said other structural unit, it is 30 mol% or less normally with respect to all the structural units which comprise a [A] polymer, and 20 mol% or less is preferable. When the content rate of the said other structural unit exceeds the said upper limit, the pattern formation property of the said radiation sensitive resin composition may fall.

  [A] The content of the polymer is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more with respect to the total solid content of the radiation-sensitive resin composition.

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

  Examples of the radical polymerization initiator include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropylene). Pionitrile), azo radical initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate; benzoyl peroxide, t-butyl hydroperoxide, And peroxide radical initiators such as cumene hydroperoxide. Of these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, and AIBN is more preferred. These radical 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, and n-decane;
Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane;
Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene;
Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene;
Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate;
Ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, 2-heptanone;
Ethers such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes;
Examples include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol, and propylene glycol monomethyl ether.
Among these, ketones and alcohols are preferable, and 2-butanone and propylene glycol monomethyl ether are more preferable. The solvent used for these polymerizations may be used alone or in combination of two or more.

  As reaction temperature in the said superposition | polymerization, 40 to 150 degreeC and 50 to 120 degreeC are preferable normally. The reaction time is usually preferably 1 hour to 48 hours and 1 hour to 24 hours.

  [A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is not particularly limited, but is preferably 1,000 or more and 50,000 or less, more preferably 2,000 or more and 30,000 or less. Preferably, 3,000 or more and 20,000 or less are more preferable, and 5,000 or more and 15,000 are particularly preferable. [A] If the Mw of the polymer is less than the lower limit, the heat resistance of the resulting resist film may be lowered. [A] If the Mw of the polymer exceeds the above upper limit, the developability of the resist film may deteriorate.

  [A] The ratio (Mw / Mn) of Mw to the number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is usually from 1 to 5, preferably from 1 to 3, more preferably from 1 to 2.5. preferable.

Mw and Mn of the polymer in this specification are values measured using gel permeation chromatography (GPC) under the following conditions.
GPC column: 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (above, manufactured by Tosoh)
Column temperature: 40 ° C
Elution solvent: Tetrahydrofuran (Wako Pure Chemical Industries)
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

  [A] The content of the low molecular weight part (refers to a part having a molecular weight of less than 1,000) in the polymer is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and 0.1% by mass. % Or less is more preferable. [A] By setting the content of the low molecular weight portion in the polymer within the above range, the rectangularity, LWR performance, resolution and depth of focus of the cross-sectional shape of the radiation-sensitive resin composition can be further improved. it can.

The content of the low molecular weight portion of the polymer in the present specification is determined by using a HPLC column (Intersil ODS-25 μm column (4.6 mmφ × 250 mm), manufactured by GL Sciences) by high performance liquid chromatography (HPLC). It is a value measured by conditions.
Elution solvent: Acrylonitrile / 0.1% by mass phosphoric acid aqueous solution Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer

<[B] Acid generator>
[B] The acid generator is a substance that generates an acid upon exposure. This acid dissociates the acid dissociable group in the [A] polymer to form a polar group such as a carboxy group, and as a result, the solubility of the [A] polymer in the developer changes. The contained form of the [B] acid generator in the radiation-sensitive resin composition may be a low molecular compound form (hereinafter also referred to as “[B] acid generator” as appropriate), as described later. It may be in the form of an acid generating group incorporated as a part, or in both forms.

  [B] Examples of the acid generator 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.

  Examples of the sulfonium salt include 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 Diphenylsulfonium camphorsulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-methanesulfonyl Phenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafur Loethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium camphorsulfonate, triphenylsulfonium 6- (1-adamantanecarbonyloxy) -1,1,2,2-tetrafluorohexane-1-sulfonate, triphenylsulfonium 2- ( And adamantane-1-ylcarbonyloxy) -1,1,3,3,3-pentafluoropropane-1-sulfonate.

  Examples of the tetrahydrothiophenium salt 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) tetrahydrothiophene Ni-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) Torahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydro Thiophenium perfluoro-n-octanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2 , 2-tetrafluoroethanesulfonate, 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-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxy Phenyl) tetrahydrothiophenium camphorsulfonate and the like.

  Examples of the iodonium salt 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. are mentioned.

  [B] Among these, the acid generator is preferably an onium salt compound, more preferably a sulfonium salt, and triphenylsulfonium 2- (adamantan-1-ylcarbonyloxy) -1,1,3,3,3- More preferred is pentafluoropropane-1-sulfonate.

  [B] As the content of the acid generator, when the [B] acid generator is a [B] acid generator, from the viewpoint of ensuring the sensitivity and developability of the radiation-sensitive resin composition, [A] 0.1 mass part or more and 30 mass parts or less are preferable with respect to 100 mass parts of unification, 0.5 mass part or more and 20 mass parts or less are more preferable, and 1 mass part or more and 15 mass parts or less are more preferable. [B] By making content of an acid generator into the said range, the sensitivity and developability of the said radiation sensitive resin composition improve. [B] 1 type (s) or 2 or more types can be used for an acid generator.

<[C] acid diffusion controller>
[C] The acid diffusion controller is the acid diffusion controller (I). The radiation-sensitive resin composition contains the acid diffusion control agent (I) in addition to the [A] polymer and the [B] acid generator, so that the LWR performance, the resolution, and the rectangular shape of the cross-sectional shape. And excellent depth of focus. [C] The acid diffusion control agent is described in the above-mentioned section of acid diffusion control agent (I). [C] 1 type (s) or 2 or more types can be used for an acid diffusion controlling agent.

[C] The content of the acid diffusion controller is preferably 1 mol% to 100 mol%, more preferably 3 mol% to 70 mol%, and more preferably 5 mol% with respect to 100 mol% of the acid generator [B]. More preferred is ˜50 mol%. [C] By making content of an acid diffusion control agent into the said range, the said radiation sensitive resin composition improves LWR performance, resolution, rectangularity of a cross-sectional shape, and depth of focus.
Further, the content of the [C] acid diffusion controller is preferably 0.1 parts by mass or more and 20 parts by mass or less, and 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the [A] polymer. Is more preferable, and 1 to 10 parts by mass is more preferable.

<Optional component>
[[D] Other acid diffusion controllers]
The radiation-sensitive resin composition may contain [D] another acid diffusion controller as necessary. In addition to the [C] acid diffusion control agent, the radiation sensitive resin composition further includes [D] another acid diffusion controller, so that LWR performance, resolution, rectangularity of the cross-sectional shape, and focus The depth can be further improved. [D] The reason why the above effect can be further improved by further containing another acid diffusion controller is not necessarily clear, but, for example, the degree of diffusion of the entire compound constituting the acid diffusion controller is determined. It can be considered that it can be adjusted. [D] The content of the other acid diffusion controller in the radiation-sensitive resin composition may be a form of an acid diffusion controller that is a low molecular compound as described later (hereinafter referred to as “[D] Other acid diffusion May be in the form of an acid diffusion control group incorporated as part of the polymer, or both.

  [D] Other acid diffusion control agents include, 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 also referred to as “nitrogen-containing compound (II)”), compounds having three nitrogen atoms (hereinafter also referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds Etc.

In the above formula (4), R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, aryl group or 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. Can be mentioned.

  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; and polymers such as dimethylaminoethylacrylamide.

  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. Can be mentioned.

  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 the nitrogen-containing heterocyclic compound include pyridines such as pyridine and 2-methylpyridine, pyrazine, pyrazole and the like.

  Moreover, the compound which has an acid dissociable group can also be used as said nitrogen-containing organic compound. Examples of the nitrogen-containing organic compound having such an acid dissociable group include N- (t-butoxycarbonyl) piperidine, N- (t-butoxycarbonyl) imidazole, N- (t-butoxycarbonyl) benzimidazole, 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 and the like can be mentioned.

  [D] As another acid diffusion controller, a photodegradable base which is exposed to light and generates a weak acid by exposure can also be used. Examples of the photodegradable base include an onium salt compound that decomposes upon exposure and loses acid diffusion controllability. Examples of the onium salt compound include a sulfonium salt compound represented by the following formula (5-1), an iodonium salt compound represented by the following formula (5-2), and the like.

In the above formulas (5-1) and (5-2), R ^{18 to} R ²² are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom. E ⁻ and Q ⁻ are each independently an anion represented by OH ⁻ , R ^α —COO ⁻ , R ^α —SO ₃ ^— or the following formula (6-3). However, ^Rα is an alkyl group, an aryl group or an aralkyl group.

In the above formula (5-3), R ²³ represents a linear or branched alkyl group having 1 to 12 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine atoms, or 1 carbon atom. It is a -12 linear or branched alkoxyl group. u is an integer of 0-2.

[D] The content of the other acid diffusion controller is [D] when the other acid diffusion controller is [D] another acid diffusion controller, and [B] 100 mol% of the acid generator. 0 mol% to 300 mol% is preferable, 5 mol% to 250 mol% is more preferable, and 10 mol% to 200 mol% is more preferable. [D] By setting the content of other acid diffusion control agents in the above range, the sensitivity, LWR performance, resolution, rectangularity of the cross-sectional shape, and depth of focus of the radiation-sensitive resin composition are further improved. Can do. [D] When the content of the other acid diffusion control agent exceeds the upper limit, the sensitivity of the radiation-sensitive resin composition may decrease.
[D] The content of the other acid diffusion control agent is preferably 0 to 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polymer [A]. 0.3 mass part-5 mass parts are further more preferable.

[[E] fluorine atom-containing polymer]
The radiation-sensitive resin composition may contain [E] fluorine atom-containing polymer (excluding those corresponding to [A] polymer). When the radiation sensitive resin composition contains the [E] fluorine atom-containing polymer, when the resist film is formed, due to the oil repellency characteristics of the [E] fluorine atom-containing polymer in the resist film, The distribution tends to be unevenly distributed in the vicinity of the resist film surface, and it is possible to suppress the elution of the acid generator, the acid diffusion controller, and the like during the immersion exposure into the immersion medium. Further, due to the water-repellent characteristics of the [E] fluorine atom-containing polymer, the advancing contact angle between the resist film and the immersion medium can 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 is increased, and high-speed scanning exposure is possible without leaving water droplets. Thus, when the said radiation sensitive resin composition contains a [E] fluorine atom containing polymer, the resist film suitable for an immersion exposure method can be formed.

  [E] The fluorine atom-containing polymer is not particularly limited as long as it is a polymer having a fluorine atom, but the fluorine atom content (mass%) than the [A] polymer in the radiation-sensitive resin composition. ) Is preferably high. [A] When the fluorine atom content is higher than that of the polymer, the degree of uneven distribution described above becomes higher, and characteristics such as water repellency and elution suppression of the resulting resist film are improved.

[E] The fluorine atom content of the fluorine atom-containing polymer is preferably 1% by mass or more, more preferably 2% by mass to 60% by mass, further preferably 4% by mass to 40% by mass, and more preferably 7% by mass to 30%. Mass% is particularly preferred. [E] When the fluorine atom content of the fluorine atom-containing polymer is less than the lower limit, the hydrophobicity of the resist film surface may be lowered. In addition, the fluorine atom content rate (mass%) of a polymer can obtain | require the structure of a polymer by < ¹³ > C-NMR spectrum measurement, and can calculate it from the structure.

  [E] The fluorine atom-containing polymer preferably has at least one selected from the group consisting of the following structural unit (Ea) and structural unit (Eb). [E] The fluorine atom-containing polymer may have one or more structural units (Ea) and structural units (Eb).

[Structural unit (Ea)]
The structural unit (Ea) is a structural unit represented by the following formula (6a). [E] A fluorine atom containing polymer can adjust a fluorine atom content rate by having a structural unit (Ea).

In the above formula (6a), R ^C represents a hydrogen atom, a methyl group or a trifluoromethyl group. G is a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO ₂ —O—NH—, —CO—NH— or —O—CO—NH—. R ^D is a monovalent chain hydrocarbon group having 1 to 6 carbon atoms having at least one fluorine atom or a monovalent aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms having at least one fluorine atom. It is.

Examples of the C1-C6 chain hydrocarbon group having at least one fluorine atom represented by ^RD include, for example, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and perfluoroethyl. Group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoropropyl group, perfluoro n-propyl group, perfluoro i-propyl group, perfluoro Examples include n-butyl group, perfluoro i-butyl group, perfluoro t-butyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, perfluorohexyl group and the like. Among these, trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,1,3,3,3-hexafluoropropyl group are preferable, 2,2,2-trifluoroethyl group Is more preferable.

Examples of the aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms having at least one fluorine atom represented by ^RD include a monofluorocyclopentyl group, a difluorocyclopentyl group, a perfluorocyclopentyl group, and a monofluorocyclohexyl group. , Difluorocyclopentyl group, perfluorocyclohexylmethyl group, fluoronorbornyl group, fluoroadamantyl group, fluorobornyl group, fluoroisobornyl group, fluorotricyclodecyl group, fluorotetracyclodecyl group and the like.

Examples of the monomer that gives the structural unit (Ea) include trifluoromethyl (meth) acrylic acid ester, 2,2,2-trifluoroethyl (meth) acrylic acid ester, and perfluoroethyl (meth) acrylic acid. Ester, perfluoro n-propyl (meth) acrylate, perfluoro i-propyl (meth) acrylate, perfluoro n-butyl (meth) acrylate, perfluoro i-butyl (meth) acrylate, 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-octafluoropentyl) (meth) acrylic acid ester, perfluorocyclohexylmethyl (meth) Acrylic acid ester, 1- (2,2,3,3,3-pentafluoropropyl) (meth) acrylic acid ester, 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 ester, fluoronorbornyl (meth) acrylic acid ester, fluoroadamantyl (Meth) acrylic acid ester, fluorobornyl (meth) acrylic acid ester, fluoroisobornyl (meth) acrylic acid ester, fluorotricyclodecyl (meth) acrylic acid ester, Le Oro tetracyclododecene decyl (meth) acrylic acid ester.
Among these, trifluoromethyl (meth) acrylic acid ester, 2,2,2-trifluoroethyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (Meth) acrylic acid esters are preferred, and 2,2,2-trifluoroethyl (meth) acrylic acid esters are more preferred.

  As a content rate of a structural unit (Ea), 5 mol%-80 mol% are preferable with respect to all the structural units which comprise a [E] fluorine atom containing polymer, 10 mol%-60 mol% are more preferable, 15 mol%-40 mol% are more preferable. By making the content rate of a structural unit (Ea) into the said range, the higher dynamic contact angle of the resist film surface can be expressed at the time of immersion exposure.

[Structural unit (Eb)]
The structural unit (Eb) is a structural unit represented by the following formula (6b). [E] Since the fluorine atom-containing polymer has a structural unit (Eb) and thus becomes more hydrophobic, it can further improve the dynamic contact angle of the resist film surface formed from the radiation-sensitive resin composition. it can.

In the above formula (6b), R ^E is a hydrogen atom, a methyl group or a trifluoromethyl group. R ²⁴ 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 a terminal on the R ²⁵ side of R ²⁴ Also includes a structure in which —CO—NH— is bonded. R ′ is a hydrogen atom or a monovalent organic group. R ²⁵ is a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, or a divalent aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms. X ² is a divalent chain hydrocarbon group having 1 to 20 carbon atoms and having at least one fluorine atom. A ¹ is 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 26.} R ²⁶ represents a hydrogen atom or a monovalent organic group. s is an integer of 1 to 3. However, when s is 2 or 3, a plurality of R ²⁵ , X ² , A ¹ and R ²⁶ may be the same or different.

It is preferable that R ²⁶ is a hydrogen atom in that the solubility of the [E] fluorine atom-containing polymer in an alkali developer can be improved.

Examples of the monovalent organic group represented by R ²⁶ include an acid dissociable group, an alkali dissociable group, or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

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

In the above formulas (6b-1) to (6b-3), R ^{24 ′} is a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. R ^E , X ² , R ²⁶ and s are as defined in the above formula (6b). When s is 2 or 3, the plurality of X ² and R ²⁶ may be the same or different.

  As a content rate of the said structural unit (Eb), 0 mol%-90 mol% are preferable with respect to all the structural units which comprise a [E] fluorine atom containing polymer, and 0 mol%-80 mol% are more preferable. 10 mol%-70 mol% are more preferable. By making the content rate of a structural unit (Eb) into the said range, 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 (Ec)]
[E] In addition to the structural units (Ea) and (Eb), the fluorine atom-containing polymer has a structural unit containing an acid-dissociable group (hereinafter also referred to as “structural unit (Ec)”). (However, those corresponding to the structural unit (Eb) are excluded). [E] Since the fluorine atom-containing polymer has the structural unit (Ec), it is possible to suppress undissolved residue of the [E] fluorine atom-containing polymer in the resist film in the developer, and as a result, Occurrence of development defects in the resist pattern can be suppressed. Examples of the structural unit (Ec) include the structural unit (I) in the above-described [A] polymer.

  As a content rate of the said structural unit (Ec), 10 mol%-90 mol% are preferable with respect to all the structural units which comprise a [E] fluorine atom containing polymer, 20 mol%-85 mol% are more preferable, More preferably, it is 25 mol% to 80 mol%. If the content ratio of the structural unit (Ec) is less than the lower limit, development defects in the resist pattern may not be sufficiently suppressed. When the content ratio of the structural unit (Ec) exceeds the above upper limit, the hydrophobicity of the resulting resist film surface may be lowered.

[Other structural units]
[E] In addition to the above structural units, the [E] fluorine atom-containing polymer has, for example, at least one structure selected from the group consisting of a structural unit containing an alkali-soluble group, a lactone structure, a cyclic carbonate structure, and a sultone structure. You may have other structural units, such as a structural unit containing and a structural unit containing a non-acid dissociable alicyclic group. As said alkali-soluble group, a carboxy group, a sulfonamide group, a sulfo group etc. are mentioned, for example. Examples of the structural unit having at least one structure selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure include the structural unit (II) in the above-mentioned [A] polymer.

  As a content rate of said other structural unit, it is 30 mol% or less normally with respect to all the structural units which comprise a [E] fluorine atom containing polymer, and 20 mol% or less is preferable. When the content rate of said other structural unit exceeds the said upper limit, the pattern formation property of the said radiation sensitive resin composition may fall.

  As content of the [E] fluorine atom containing polymer in the said radiation sensitive resin composition, 0-20 mass parts is preferable with respect to 100 mass parts of [A] polymer, and 0.5 mass part-15 parts. A mass part is more preferable, and 1 mass part-10 mass parts are still more preferable. [E] If the content of the fluorine atom-containing polymer exceeds the above upper limit, the pattern-forming property of the radiation-sensitive resin composition may be lowered.

<[F] solvent>
The radiation-sensitive resin composition usually contains a [F] solvent. [F] Solvent can dissolve or disperse at least [A] polymer, [B] acid generator and [C] acid diffusion controller, and [D] other acid diffusion controller contained as desired. If it is a solvent, it will not specifically limit.

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

As an alcohol solvent, for example,
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, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furf Alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
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;
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-ethylbutyl 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.

As an ether solvent, for example,
Dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether;
Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran;
Aromatic ring-containing ether solvents such as diphenyl ether and anisole (methylphenyl ether) are exemplified.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone (methyl-n-pentyl ketone), and 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 and the like can be mentioned.

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

Examples of ester solvents include:
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-pentyl acetate, 3-methoxy acetate Acetate solvents such as butyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, and n-nonyl acetate;
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 diethyl carbonate;
Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, ethyl lactate N-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

Examples of the hydrocarbon solvent include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, and cyclohexane. , Aliphatic hydrocarbon solvents such as methylcyclohexane;
Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene and 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 further preferable. The radiation-sensitive resin composition may contain one or more [F] solvents.

[Other optional ingredients]
The said radiation sensitive resin composition may contain other arbitrary components other than said [A]-[F]. Examples of the other optional components include uneven distribution accelerators, surfactants, alicyclic skeleton-containing compounds, and sensitizers. Each of these other optional components may be used alone or in combination of two or more.

(Uniformity promoting agent)
The uneven distribution accelerator has the effect of segregating the [E] fluorine atom-containing polymer more efficiently on the resist film surface. The amount of the [E] fluorine atom-containing polymer added can be reduced by adding this uneven distribution accelerator to the radiation sensitive resin composition. Therefore, elution of components from the resist film to the immersion liquid can be further suppressed without impairing the cross-sectional rectangularity, LWR performance, resolution, depth of focus, and other characteristics, and immersion exposure can be performed at a higher speed by high-speed scanning. As a result, the hydrophobicity of the resist film surface that suppresses immersion-derived defects such as watermark defects can be improved. Examples of such an uneven distribution promoter include low molecular compounds having a relative dielectric constant of 30 or more and 200 or less and a boiling point at 1 atm of 100 ° C. or more. Specific examples of such compounds include lactone compounds, carbonate compounds, nitrile compounds, and polyhydric alcohols.

  Examples of the lactone compound include γ-butyrolactone, valerolactone, mevalonic lactone, norbornane lactone, and the like.

  Examples of the carbonate compound include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, and the like.

Examples of the nitrile compound include succinonitrile.
Examples of the polyhydric alcohol include glycerin.

  Of these, the ubiquitous accelerator is preferably a lactone compound, and more preferably γ-butyrolactone.

  As content of the uneven distribution promoter in the said radiation sensitive resin composition, 10 mass parts-500 mass parts are preferable with respect to 100 mass parts of total amounts of a polymer, 15 mass parts-300 mass parts are more preferable, 20 mass parts-100 mass parts are more preferable.

(Surfactant)
Surfactants have the effect of improving coatability, striation, developability, and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate. Nonionic surfactants such as stearate; commercially available products include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173 (above, manufactured by DIC), Florard FC430, FC431 (above, Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, manufactured by Asahi Glass), etc. It is done. As content of surfactant in the said radiation sensitive resin composition, it is 2 mass parts or less normally with respect to 100 mass parts of [A] polymers.

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

Examples of the alicyclic skeleton-containing compound include adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid t-butyl;
Deoxycholic acid esters such as t-butyl deoxycholate, t-butoxycarbonylmethyl deoxycholic acid, 2-ethoxyethyl deoxycholic acid;
Lithocholic acid esters such as t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid;
3- [2-Hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] nonane, and the like. As content of the alicyclic skeleton containing compound in the said radiation sensitive resin composition, it is 5 mass parts or less normally with respect to 100 mass parts of [A] polymers.

(Sensitizer)
A sensitizer exhibits the effect | action which increases the production amount of the acid from [B] acid generator etc., and there exists an effect which improves the "apparent sensitivity" of the said radiation sensitive resin composition.

  Examples of the sensitizer include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. These sensitizers may be used alone or in combination of two or more. As content of the sensitizer in the said radiation sensitive resin composition, it is 2 mass parts or less normally with respect to 100 mass parts of [A] polymers.

<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition includes, for example, a predetermined ratio of [A] polymer, [B] acid generator, [C] acid diffusion controller, optional component contained as necessary, and [F] solvent. Can be prepared by mixing. The radiation-sensitive resin composition is preferably filtered after mixing with, for example, a filter having a pore size of about 0.2 μm. As solid content concentration of the said radiation sensitive resin composition, 0.1 mass%-50 mass% are preferable, 0.5 mass%-30 mass% are more preferable, 1 mass%-20 mass% are more preferable.

<Resist pattern formation method>
The resist pattern forming method is:
(1) A step of forming a resist film on a substrate using the radiation sensitive resin composition,
(2) a step of exposing the resist film; and (3) a step of developing the exposed resist film.

  According to the resist pattern forming method, since the radiation-sensitive resin composition described above is used, a resist pattern having a high LDO with a small LWR, excellent cross-sectional rectangularity, and high resolution while exhibiting a wide depth of focus. Can be formed. Hereinafter, each step will be described.

[(1) Process]
In step (1), a resist film is formed using the radiation-sensitive resin composition. Examples of the substrate on which the resist film is formed include a silicon wafer, silicon dioxide, a wafer coated with an antireflection film, and the like. Examples of the method for applying the radiation sensitive resin composition include methods such as spin coating, cast coating, and roll coating. It is preferable to evaporate and remove the solvent in the coating film by pre-baking (PB) the coating film formed by the above application. As PB temperature, it is 60 to 140 degreeC normally, and 80 to 120 degreeC is preferable. The PB time is usually 5 seconds to 600 seconds, and preferably 10 seconds to 300 seconds.

[(2) Process]
In the step (2), the resist film formed in the step (1) is exposed. This exposure is performed by irradiating exposure light through a photomask or the like (in some cases through an immersion medium such as water). Examples of exposure light include electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and γ rays; and charged particle beams such as electron beams and α-rays, depending on the line width of the target pattern. Can be mentioned. Among these, far ultraviolet rays, extreme ultraviolet rays, and electron beams are preferable, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV (13.5 nm), and electron beams are more preferable, and ArF excimer laser light. An electron beam is more preferable.

  After the above exposure, post-exposure baking (PEB) is performed to promote dissociation of the acid-dissociable group of the [A] polymer by the acid generated from the [B] acid generator by the exposure in the exposed portion of the resist film. It is preferable to make it. This PEB can surely cause a difference in solubility in the developer between the exposed portion (exposed portion) and the unexposed portion (unexposed portion). As PEB temperature, it is 50 to 180 degreeC normally, and 80 to 130 degreeC is preferable. The PEB time is usually 5 seconds to 600 seconds, and preferably 10 seconds to 300 seconds.

  When performing immersion exposure, before the step (2), in order to protect the direct contact between the immersion liquid and the resist film, an immersion protective film insoluble in the immersion liquid is provided on the resist film. May be. Examples of the immersion protective film include a solvent peeling type protective film that peels off with a solvent before the step (3) (see, for example, JP-A-2006-227632), and a developer peeling type that peels off simultaneously with the development in the step (3). Any of the protective films (see, for example, WO2005-069076 and WO2006-035790) may be used. However, from the viewpoint of throughput, it is preferable to use a developer peeling type immersion protective film.

[(3) Process]
In step (3), the resist film exposed in step (2) is developed. Thereby, a predetermined resist pattern is formed. The development method may be alkali development or organic solvent development. Usually, a positive resist pattern is formed by alkali development, and a negative resist pattern is formed by organic solvent development. After the development, it is common to wash with water or a rinse solution such as alcohol and dry.

As the developer,
In the case of alkali development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine , Ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4 .3.0] -5 aqueous solution in which at least one alkaline compound such as 5-nonene is dissolved. Among these, a TMAH aqueous solution is preferable, and a 2.38 mass% TMAH aqueous solution is more preferable.
In the case of organic solvent development, organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, alcohol solvents, etc., or solvents containing organic solvents can be mentioned. As said organic solvent, the 1 type (s) or 2 or more types of the solvent enumerated as [F] solvent of the above-mentioned radiation sensitive resin composition are mentioned, for example. Among these, ester solvents and ketone solvents are preferable. As the ester solvent, an acetate solvent is preferable, and n-butyl acetate is more preferable. As the ketone solvent, a chain ketone is preferable, and 2-heptanone is more preferable.

<Compound>
The compound is compound (I). Since the compound has the above-described properties, it can be suitably used as an acid diffusion control agent. The radiation-sensitive resin composition containing the compound has LWR performance, resolution, rectangularity of the cross-sectional shape, and depth of focus. Excellent.

<Method for producing compound>
The method for producing the compound of the present invention comprises:
The manufacturing method of the compound represented by the said Formula (1 ') which has a process with which the compound represented by the said Formula (ia) and the compound represented by the said Formula (ib) are made to react, and the said It is a manufacturing method of the compound represented by following formula (2 ') which has a process with which the compound represented by formula (ia') and the compound represented by said formula (ib) are made to react.
Since the manufacturing method of the said compound has the said process, the said compound can be obtained simply and with a sufficient yield.
The said compound and the manufacturing method of the said compound are demonstrated in the term of the said acid diffusion control agent (I).

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measuring method of various physical property values is shown below.

[Mw, Mn and Mw / Mn]
Mw and Mn of the polymer were measured by GPC using GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL, manufactured by Tosoh Corporation) under the following analysis conditions. Mw / Mn was calculated from the measurement results of Mw and Mn.
(Analysis conditions)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Column temperature: 40 ° C
Detector: Differential refractometer Standard material: Monodisperse polystyrene

[Low molecular weight partial content]
[A] The content (mass%) of the low molecular weight portion (referring to a portion having a molecular weight of less than 1,000) in the polymer is HPLC column (Intersil ODS-25 μm column (4.6 mmφ × 250 mm), manufactured by GL Sciences) Was measured by HPLC under the following analytical conditions.
(Analysis conditions)
Elution solvent: Acetonitrile / 0.1% by mass phosphoric acid aqueous solution Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer

^[1 H-NMR analysis and ¹³ C-NMR Analysis
Of ¹ H-NMR analysis and ¹³ C-NMR analysis of the compound, ¹³ C-NMR analysis to determine the respective structural units content and fluorine atom content of the polymer, nuclear magnetic resonance apparatus (JNM-ECX400, manufactured by JEOL ).

<Synthesis of Compound (I)>
Compound (I) was synthesized according to the following reaction scheme. The following compounds (i-1) to (i-6) were synthesized according to the following scheme (A), and the following compound (i-7) was synthesized according to the following scheme (B).

In the above scheme (A),
R ² is a cyclohexyl group or a phenyl group.
R ⁵ and R ⁶ are an ethyl group or are bonded together to form a piperidine group or a decahydroquinoline group together with the nitrogen atom to which they are bonded.
Y is —CO— or —SO ₂ —.
L is —CO— or —CH ₂ —.

In the above scheme (B),
R ¹ and R ² are bonded to each other to form a morpholine structure together with the nitrogen atom to which they are bonded.
R ³ is a methyl group.
R ⁵ and R ⁶ are bonded to each other to form a piperidine structure together with the nitrogen atom to which they are bonded.
Y is -CO-.

[Example 1]
A 100 mL eggplant-shaped flask was charged with 3.58 g (20 mmol) of N-cyclohexylmaleimide, 1.87 g (22 mmol) of piperidine and 10 g of toluene, and stirred at room temperature for 28 hours to be reacted. Water was washed 5 times by adding a liquid to the resulting reaction solution and then performing a liquid separation operation. The reaction solution after washing with water was dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a pale yellow oil. The obtained pale yellow oil was purified by column chromatography to obtain 4.33 g of the compound (i-1) represented by the following formula (i-1) as a colorless oil (yield 81.9%). ).

[Examples 2 to 4]
In Example 1, in place of N-cyclohexylmaleimide, N-phenylmaleimide was used, and piperidine, diethylamine or decahydroquinoline was used as the amine compound, and in the same manner as in Example 1, the following formula (i- The compounds represented by 2) to (i-4) were synthesized.

[Examples 5 and 6]
In Example 1, Example 1 was used except that N-cyclohexyl-4,5-didehydrobutyrolactam or N-cyclohexyl-4,5-didehydropropane sultam was used instead of N-cyclohexylmaleimide. Similarly, the compounds represented by the following formula (i-5) and the following formula (i-6) were respectively synthesized.

[Example 7]
In Example 1, a compound represented by the following formula (i-7) was synthesized in the same manner as in Example 1 except that N-methacryloylmorpholine was used instead of N-cyclohexylmaleimide.

<Synthesis of polymer>
Each monomer used for the synthesis of [A] polymer and [E] fluorine atom-containing polymer is shown below.

[[A] Synthesis of polymer]
[Synthesis Example 1]
9.01 g (50 mol%) of the compound (M-1) and 10.99 g (50 mol%) of the compound (M-2) were dissolved in 40 g of 2-butanone, and 0.81 g of AIBN as a radical polymerization initiator ( A monomer solution was prepared by dissolving 5 mol% of the total number of moles of the above compound. A 100 mL three-necked flask containing 20 g of 2-butanone was purged with nitrogen for 30 minutes, then heated to 80 ° C. with stirring, and the prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The dripping start was set as the polymerization reaction start time, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization reaction, the polymerization reaction solution was cooled with water and cooled to 30 ° C. or lower. The cooled polymerization reaction liquid was put 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 powder polymer (A-1) (15.6 g, yield). 78%). Mw of the polymer (A-1) was 7,200, and Mw / Mn was 1.52. As a result of ¹³ C-NMR analysis, the content ratios of the structural unit derived from (M-1) and the structural unit derived from (M-2) were 50.2 mol% and 49.8 mol%, respectively. The content rate of the low molecular weight part in a polymer (A-1) was 0.04 mass%.

[Synthesis Example 2]
After dissolving 55.0 g of the compound (M-4), 45.0 g of the compound (M-5), 4 g of AIBN as a radical polymerization initiator and 1 g of t-dodecyl mercaptan as a chain transfer agent in 100 g of propylene glycol monomethyl ether. The polymerization reaction was carried out for 16 hours while maintaining the reaction temperature at 70 ° C. under a nitrogen atmosphere. After the completion of the polymerization reaction, the polymerization reaction solution was dropped into 1,000 g of n-hexane to coagulate and purify the resulting polymer. Next, 150 g of propylene glycol monomethyl ether was added to the polymer again, and then 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 the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting polymer was dissolved in 150 g of acetone, then dropped into 2,000 g of water to solidify, and the resulting white powder was filtered off and filtered at 50 ° C. It was made to dry for a time and the polymer (A-2) of the white powder was obtained (65.7g, yield 76.6%). The polymer (A-2) had Mw of 10,000 and Mw / Mn of 2.1. As a result of ¹³ C-NMR analysis, the content ratios of the structural unit derived from p-hydroxystyrene and the structural unit derived from (M-5) were 65.4 mol% and 34.6 mol%. The content of the low molecular weight portion in the polymer (A-2) was 0.05% by mass.

[[E] Synthesis of fluorine atom-containing polymer]
[Synthesis Example 3]
79.9 g (70 mol%) of the above compound (M-1) and 20.91 g (30 mol%) of the compound (M-3) were dissolved in 100 g of 2-butanone, and dimethyl 2 as a radical polymerization initiator was further dissolved. , 2′-Azobisisobutyrate 4.77 g was dissolved to prepare a monomer solution. A 1,000 mL three-necked flask containing 100 g of 2-butanone was purged with nitrogen for 30 minutes, then heated to 80 ° C. with stirring, and the prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The dripping start was set as the polymerization reaction start time, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization reaction, the polymerization reaction solution was cooled with water and cooled to 30 ° C. or lower. After transferring the polymerization reaction liquid to a 2 L separatory funnel, the polymerization reaction liquid 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 shaken and allowed to stand for 30 minutes. Next, after recovering the lower layer, solvent substitution was performed to obtain a propylene glycol monomethyl ether acetate solution of the polymer (E-1) (yield 60%). Mw of the polymer (E-1) was 7,200, and Mw / Mn was 2.00. As a result of ¹³ C-NMR analysis, the content ratios of the structural unit derived from (M-1) and the structural unit derived from (M-3) were 71.1 mol% and 28.9 mol%. The low molecular weight partial content of the polymer (E-1) was 0.07% by mass.

<Preparation of radiation-sensitive resin composition>
Each component used for preparation of a radiation sensitive resin composition is shown below.

[[B] acid generator]
B-1: Triphenylsulfonium 2- (adamantan-1-ylcarbonyloxy) -1,1,3,3,3-pentafluoropropane-1-sulfonate (compound represented by the following formula (B-1))

[[C] acid diffusion controller]
Compounds represented by the above formulas (i-1) to (i-7), and compounds represented by the following formulas (ci-1) and (ci-2)

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

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

[Example 8]
[A] 100 parts by mass of (A-1) as a polymer, [B] 8.5 parts by mass of (B-1) as an acid generator, [C] (i-1) 30 as an acid diffusion controller Mol% (molar ratio to 100 mol% of [B] acid generator), [E] 3 parts by mass of (E-1) as a fluorine atom-containing polymer, (F-1) 2,240 as [F] solvent A radiation-sensitive resin composition (J-1) was prepared by mixing 30 parts by mass of (G-1) as a [G] uneven distribution accelerator, and 960 parts by mass of (F-2).

[Examples 9 to 14 and Comparative Examples 1 and 2]
The radiation sensitive resin compositions (J-2) to (J-7) and (CJ-1) and (CJ-1) and (CJ-1) were used in the same manner as in Example 8 except that the components having the types and contents shown in Table 1 were used. CJ-2) was prepared.

<Formation of resist pattern>
[In the case of ArF exposure]
(Alkali development)
Using a spin coater (CLEAN TRACK ACT12, manufactured by Tokyo Electron) on the surface of a 12-inch silicon wafer, a lower antireflection film forming composition (ARC66, manufactured by Brewer Science) was applied, and then heated at 205 ° C. for 60 seconds. As a result, a lower antireflection film having a thickness of 105 nm was formed. On the lower antireflection film, each radiation sensitive resin composition was applied using the spin coater, and PB was performed at 90 ° C. for 60 seconds. Thereafter, it was cooled at 23 ° C. for 30 seconds to form a resist film having a thickness of 90 nm. Next, this resist film is 40 nm in an optical condition of NA = 1.3 and dipole (Sigma 0.977 / 0.782) using an ArF excimer laser immersion exposure apparatus (NSR-S610C, manufactured by NIKON). Exposure was through a line and space (1L1S) mask pattern. After the exposure, PEB was performed at 90 ° C. for 60 seconds. Then, it developed with the 2.38 mass% TMAH aqueous solution, wash | cleaned and dried with water, and formed the positive resist pattern.

(Organic solvent development)
In the formation of the resist pattern by the above [alkaline development], the above [alkaline development] except that n-butyl acetate was used instead of the 2.38 mass% TMAH aqueous solution as a developer and no washing with water was performed. In the same manner as described above, a negative resist pattern was formed.

<Evaluation>
In each of the alkali development and organic solvent development, each radiation-sensitive resin composition was evaluated by measuring each resist pattern formed. In each case, the exposure amount for forming the 40 nm 1L1S pattern by the exposure through the 40 nm 1L1S mask pattern was set as the optimum exposure amount (Eop). A scanning electron microscope (S-9380, manufactured by Hitachi High-Technologies Corp.) was used for measuring the resist pattern formed by this method. As “comparative examples” to be compared with the examples in the following evaluation, examples 1 to 4 and 7 were set to comparative example 1, and examples 5 and 6 were set to comparative example 2. The evaluation results are shown in Table 2. “-” In Table 2 indicates a criterion for evaluation.

[LWR performance]
The resist pattern formed in the Eop was observed from above the pattern using the scanning electron microscope. A total of 50 line widths were measured at arbitrary points, and a 3-sigma value was obtained from the distribution of the measured values, and this was defined as LWR performance (nm). LWR performance indicates that the smaller the value, the better. The LWR performance is “good” when the LWR performance improvement is 10% or more (meaning that the LWR performance value is 90% or less) compared to the comparative example, and the LWR performance improvement is less than 10%. Was evaluated as “bad”.

[Resolution]
The minimum resist pattern dimension resolved in the above Eop was defined as resolution (nm). The smaller the value, the better the resolution. The resolution is 10% or more in comparison with the comparative example (which means that the resolution value is 90% or less). Those that were improved in resolution were evaluated as “bad”.

[Rectangularity of the cross-sectional shape]
The cross-sectional shape of the resist pattern resolved in the Eop was observed, and the line width Lb in the middle of the resist pattern in the height direction and the line width La at the top of the resist film were measured. The rectangularity of the cross-sectional shape is “good” when 0.9 ≦ (La / Lb) ≦ 1.1, and (La / Lb) <0.9 or 1.1 <(La / Lb). The case was rated as “bad”.

[Depth of focus]
In the resist pattern resolved in the above Eop, the dimension when the focus is changed in the depth direction is observed, and the margin in the depth direction where the pattern dimension falls within 90% to 110% of the standard without any bridge or residue. Degree was the depth of focus (nm). The depth of focus indicates that the larger the value, the better. Depth of focus is 10% or better compared to the comparative example (meaning that the depth of focus value is 110% or more). Was evaluated as “bad”.

  As is clear from the results of Table 2, in ArF exposure, the radiation-sensitive resin compositions of the examples were compared with the radiation-sensitive resin compositions of the comparative examples, both in the case of alkali development and organic solvent development. In other words, it is excellent in resolution, rectangularity of the cross-sectional shape, and depth of focus.

<Preparation of radiation-sensitive resin composition>
[In the case of electron beam irradiation]
[Example 15]
[A] 100 parts by mass of (A-2) as a polymer, [B] 20 parts by mass of (B-1) as an acid generator, [C] (i-1) 30 mol% as an acid diffusion controller (Molar ratio to [B] acid generator), and (F-1) 4,280 parts by mass and (F-2) 1,830 parts by mass as solvent [F] are mixed to produce a radiation sensitive resin composition. (J-8) was prepared.

[Examples 16 to 21 and Comparative Examples 3 and 4]
Each radiation sensitive resin composition (J-9) to (J-14) and (CJ-3) was operated in the same manner as in Example 1 except that each component having the type and content shown in Table 3 below was used. ) And (CJ-4) were prepared.

<Formation of resist pattern>
Using a spin coater (CLEAN TRACK ACT8, manufactured by Tokyo Electron) on the surface of an 8-inch silicon wafer, each radiation sensitive resin composition was applied, and PB was performed at 90 ° C. for 60 seconds. Thereafter, it was cooled at 23 ° C. for 30 seconds to form a resist film having a thickness of 50 nm. Next, the resist film was irradiated with an electron beam using a simple electron beam drawing apparatus (HL800D, manufactured by Hitachi, Ltd., output: 50 KeV, current density: 5.0 amperes / cm ² ). After irradiation, PEB was performed at 130 ° C. for 60 seconds. Thereafter, development was performed at 23 ° C. for 30 seconds using a 2.38 mass% TMAH aqueous solution, washed with water, and dried to form a positive resist pattern.

  For each formed resist pattern, among the evaluations in the above [ArF exposure], the LWR performance, the resolution, and the rectangular shape of the cross-sectional shape are measured by the same method as described above, and the radiation-sensitive resin composition is evaluated. It was. As “comparative examples” to be compared with examples, comparative examples 3 were used for examples 15 to 18 and 21, and comparative example 4 was used for examples 19 and 20. The evaluation results are shown in Table 3. “-” In Table 3 indicates that it is a criterion for evaluation.

  As is clear from the results in Table 3, in the case of electron beam irradiation, the radiation-sensitive resin compositions of the examples had LWR performance, resolution, and cross-sectional shape as compared with the radiation-sensitive resin compositions of the comparative examples. It can be said that the rectangularity is excellent.

According to the acid diffusion controller of the present invention, a radiation sensitive resin composition containing the acid diffusion control agent, and a resist pattern forming method using the radiation sensitive resin composition, the LWR is small and the resolution is high while exhibiting a wide depth of focus. And a resist pattern that is excellent in the rectangular shape of the cross-sectional shape can be formed. Moreover, the compound of this invention can be used suitably as the said acid diffusion controlling agent. Therefore, they can be suitably used for pattern formation in semiconductor device manufacturing, which is expected to become increasingly finer in the future.

Claims (5)

An acid diffusion controller for a radiation-sensitive resin composition comprising a compound represented by the following formula (1).

(In the formula (1),
R ¹ is either a monovalent chain-like hydrocarbon group having 1 to 20 carbon atoms, bound to R ^2, A Zaoki service cycloalkane monocyclic ring members 5-10 together with the nitrogen atom to which they are attached or to form a structure, or combines with R ^3, the nitrogen atom to which R ¹ is attached, lactam ring structure ring members 5 to 10 together with a carbon atom, and Y to R ³ are attached sultam ring structure or an imide ring Forming a structure.
R ² is a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms , or is bonded to R ¹ and these are bonded. to form a monocyclic a Zaoki Sa cycloalkane structure ring members 5-10 together with a nitrogen atom.
R ³ is a hydrogen atom, or either a monovalent chain-like hydrocarbon group having a carbon number of 1-4, or combine with R ^1, the carbon atom to which the nitrogen atom ^{to which R 1} is bonded, is ^{R 3} are attached, and lactam ring structure ring members 5-10 with Y, that form a sultam ring structure or an imide ring structure.
R ⁴ is hydrogen atom.
n is 1 or 2. When n is 2, the plurality of R ³ and R ⁴ may be the same or different.
R ⁵ and R ⁶ are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, or together with the nitrogen atom to which R ⁵ and R ⁶ are bonded to each other. forming a azacycloalkane structure ring members 5-10.
X is a single bond or a divalent chain hydrocarbon group having 1 to 4 carbon atoms.
Y is —CO— or —SO ₂ —. ) The acid diffusion controller according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (2).

(In the formula (2),
R ² is a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms .
R ^3a is a hydrogen atom or a monovalent chain hydrocarbon group having 1 to 4 carbon atoms.
R ^4a and R ^4b are hydrogen atoms.
R ⁷ is a (k + 2) -valent hydrocarbon group.
k is an integer of 0-6.
p is 0 or 1.
R ⁸ is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
When k is 2 or more, the plurality of R ⁸ may be the same or different.
Z is —CO— or —SO ₂ —.
m is 0 or 1.
R ⁵ , R ⁶ , X and Y are as defined in the above formula (1). ) [A] a polymer having an acid dissociable group,
A radiation-sensitive resin composition containing [B] an acid generator and [C] the acid diffusion controller according to claim 1 or 2 . [D] The radiation-sensitive resin composition according to claim 3 , further comprising an acid diffusion controller other than the [C] acid diffusion controller. (1) A step of forming a resist film using the radiation-sensitive resin composition according to claim 3 or claim 4 ,
(2) A resist pattern forming method comprising: exposing the resist film; and (3) developing the exposed resist film.