JP5933308B2 - Chemically amplified resist composition, resist film using the same, resist-coated mask blanks, resist pattern forming method, and electronic device manufacturing method - Google Patents

Description

  The present invention is a chemical that can form a highly refined pattern using an electron beam or extreme ultraviolet rays, which is suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other fabrication processes. The present invention relates to an amplification resist composition, a resist film using the same, a resist coating mask blank, a resist pattern forming method, and a photomask. In particular, the present invention relates to a chemically amplified resist composition used in a process using a substrate having a specific base film, a resist film using the same, a resist-coated mask blank, a resist pattern forming method, and a photomask.

  The chemically amplified resist composition generates an acid in the exposed area by irradiation with radiation such as far-ultraviolet light, and the acid-catalyzed reaction causes the solubility of the active radiation irradiated area and non-irradiated area in the developer. This is a pattern forming material for changing the pattern to form a pattern on the substrate.

  When a KrF excimer laser is used as an exposure light source, a resin having a basic skeleton of poly (hydroxystyrene) having a small absorption mainly in the 248 nm region is used as a main component. A pattern is formed, which is a better system than the conventional naphthoquinone diazide / novolak resin system.

On the other hand, when a further short wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group exhibits a large absorption in the 193 nm region. It wasn't.
For this reason, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed.

A triphenylsulfonium salt is generally known as an acid generator that is a main constituent of a chemically amplified resist.
In addition, in order to provide a chemically amplified resist composition in which the photochemical reaction is amplified and the photosensitive speed is remarkably improved, an acid is newly generated by the acid generated from the acid generator together with the acid generator as described above. It is known to use an acid proliferating agent (see, for example, Patent Document 1).
As an acid proliferating agent, an acid proliferating agent having a structure in which a sulfonyloxy group and a hydroxy group are linked via three carbon atoms is known. For example, Patent Document 2 and Non-Patent Document 1 disclose the use of an acid growth agent having such a specific structure in a positive chemically amplified resist composition. Patent Document 3 discloses a positive chemically amplified resist composition containing a resin having such a specific structure.

  In addition, microfabrication using a resist composition is not only directly used for the production of integrated circuits, but also has recently been applied to the production of so-called imprint mold structures (for example, Patent Document 4 and non-patent documents). Reference 2). Therefore, high sensitivity and high resolution (for example, high resolution, excellent pattern shape, small line edge roughness (LER)), good dry etching resistance, excellent scum characteristics, and excellent stability over time are satisfied at the same time. It is an important issue.

JP-A-8-248561 JP 2011-33729 A JP 2011-53624 A JP 2008-162101 A

J. et al. Am. Chem. Soc. 2009, 131 (29), 9862-9863 Nanoimprint Basics and Technology Development / Application Development-Nanoimprint Fundamental Technologies and Latest Technology Deployment-Editing: Yoshihiko Hirai Frontier Publishing (issued in June 2006)

The object of the present invention is to provide high sensitivity, high resolution (for example, high resolution, excellent pattern shape, small line edge roughness (LER)), high aging stability, low occurrence of scum and good dry etching resistance. Another object is to provide a chemically amplified resist composition capable of forming a satisfactory pattern at the same time. In particular, since the acid proliferating agent represented by the general formula (I) has an ester group, the balance between sensitivity and stability over time is good, and when the acid proliferating agent is acid-decomposed, carboxylic acid is generated. An object of the present invention is to provide a chemically amplified resist composition that is particularly excellent in improving sensitivity.
Another object of the present invention is to provide a resist film, a resist-coated mask blank, a resist pattern forming method, and a photomask using the chemically amplified resist composition.

上記一般式（Ｉ）中、Ｒ _１ 〜Ｒ _５ の各々は、水素原子又は置換基を表す。Ｒ _１ 〜Ｒ _５ は、それらの２以上が互いに結合して、環を形成していてもよい。Ｒ _６ は、置換基を表す。
Ａは１価の有機基を表す。
＜２＞
（Ａ）下記一般式（Ｉ）で表される化合物、（Ｂ）活性光線又は放射線の照射により酸を発生する化合物、及び、（Ｃ）酸の作用により分解し、アルカリ可溶性基を生じる基を有する樹脂を含有する、ポジ型のパターン形成用である、化学増幅型レジスト組成物であって、前記樹脂（Ｃ）が下記式（ａ）に示す繰り返し単位を有する樹脂である、化学増幅型レジスト組成物。

上記一般式（Ｉ）中、Ｒ _１ 〜Ｒ _５ の各々は、水素原子又は置換基を表す。Ｒ _１ 〜Ｒ _５ は、それらの２以上が互いに結合して、環を形成していてもよい。Ｒ _６ は、置換基を表す。
Ａは１価の有機基を表す。

＜３＞
前記樹脂（Ｃ）における酸の作用により分解し、アルカリ可溶性基を生じる基が、前記アルカリ可溶性基の水素原子をアセタール基で置換した基である、上記＜２＞に記載の化学増幅型レジスト組成物。
＜４＞
前記樹脂（Ｃ）が、下記一般式（Ａ）で表される繰り返し単位を有する樹脂である、上記＜２＞に記載の化学増幅型レジスト組成物。

式中、Ｒ_０１、Ｒ_０２及びＲ_０３は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。Ａｒ_１はアルキレン基又は芳香環基を表す。Ｒ_０３がアルキレン基であり、芳香環基としてのＡｒ_１と結合することにより、−Ｃ−Ｃ−鎖と共に、環を形成していてもよい。
ｎ個のＹは、各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Ｙの
少なくとも１つは、酸の作用により脱離する基を表す。
ｎは、１〜４の整数を表す。
＜５＞
前記一般式（Ａ）におけるＹとしての酸の作用により脱離する基が、下記一般式（Ｂ）で表される構造である、上記＜４＞に記載の化学増幅型レジスト組成物。

式中、Ｌ_１及びＬ_２は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基又はアラルキル基を表す。
Ｍは、単結合又は２価の連結基を表す。
Ｑは、アルキル基、シクロアルキル基、環状脂肪族基、芳香環基、アミノ基、アンモニウム基、メルカプト基、シアノ基又はアルデヒド基を表す。なお、これら環状脂肪族基及び芳香環基は、ヘテロ原子を含んでいてもよい。
なお、Ｑ、Ｍ、Ｌ_１の少なくとも２つが互いに結合して、５員又は６員環を形成していてもよい。
＜６＞
前記酸の作用により分解し、アルカリ可溶性基を生じる基を有する樹脂（Ｃ）が下記一般式（２）で表される繰り返し単位を有する樹脂である、上記＜２＞〜＜５＞のいずれか１項に記載の化学増幅型レジスト組成物。

上記一般式（２）中、Ｒ_１２は、水素原子又はメチル基を表す。
Ａｒは、芳香族環を表す。
＜７＞
（Ａ）下記一般式（Ｉ）で表される化合物、（Ｂ）活性光線又は放射線の照射により酸を発生する化合物、及び、（Ｄ）架橋剤を含有する、ネガ型のパターン形成用である、化学増幅型レジスト組成物。

上記一般式（Ｉ）中、Ｒ_１〜Ｒ_５の各々は、水素原子又は置換基を表す。Ｒ_１〜Ｒ_５は、それらの２以上が互いに結合して、環を形成していてもよい。Ｒ_６は、置換基を表す。
Ａは１価の有機基を表す。
＜８＞
前記架橋剤（Ｄ）が、ヒドロキシメチル基又はアルコキシメチル基を分子内に２個以上有する化合物である、上記＜７＞に記載の化学増幅型レジスト組成物。
＜９＞
（Ｅ）フェノール性水酸基を有する化合物を更に含有する、上記＜７＞又は＜８＞に記載の化学増幅型レジスト組成物。
＜１０＞
前記フェノール性水酸基を有する化合物（Ｅ）が、下記一般式（２）で表される繰り返し単位を有する高分子化合物である、上記＜９＞に記載の化学増幅型レジスト組成物。

上記一般式（２）中、Ｒ_１２は、水素原子又はメチル基を表す。
Ａｒは、芳香族環を表す。
＜１１＞
電子線又は極紫外線露光用である、上記＜１＞〜＜１０＞のいずれか１項に記載の化学増幅型レジスト組成物。
＜１２＞
前記化合物（Ｂ）が、活性光線又は放射線の照射により、体積２００Å^３以上の大きさの酸を発生する化合物である、上記＜１＞〜＜１１＞のいずれか１項に記載の化学増幅型レジスト組成物。
＜１３＞
上記＜１＞〜＜１２＞のいずれか１項に記載の化学増幅型レジスト組成物により形成されたレジスト膜。
＜１４＞
上記＜１３＞に記載のレジスト膜を塗布した、レジスト塗布マスクブランクス。
＜１５＞
上記＜１３＞に記載のレジスト膜を露光すること、及び、前記露光された膜を現像することを含む、レジストパターン形成方法。
＜１６＞
上記＜１４＞に記載のレジスト塗布マスクブランクスを露光すること、及び、前記露光されたマスクブランクスを現像することを含む、レジストパターン形成方法。
＜１７＞
上記＜１５＞に記載のレジストパターン形成方法を含む、電子デバイスの製造方法。
尚、本発明は、上記＜１＞〜＜１７＞に係る発明であるが、以下、その他についても参考のため記載した。 As a result of intensive studies, the present inventors have found that the above object can be achieved by a chemically amplified resist composition containing an acid proliferating agent having a specific structure. The present invention has been made based on this finding.
That is, the present invention is as follows.
<1>
(A) A chemically amplified resist composition comprising a compound represented by the following general formula (I), and (B) a compound that generates an acid upon irradiation with actinic rays or radiation, wherein the compound (A) is A chemically amplified resist composition that is a compound that generates an acid having a volume of 200 ³ or more.

In the general formula (I), each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group.
<2>
(A) a compound represented by the following general formula (I), (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a group that decomposes by the action of an acid to generate an alkali-soluble group. A chemically amplified resist composition for forming a positive pattern containing a resin having a resin, wherein the resin (C) is a resin having a repeating unit represented by the following formula (a) Composition.

In the general formula (I), each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group.

< 3 >
Decomposing by the action of an acid before Symbol resin (C), a group generate an alkali-soluble group, the alkali hydrogen atom soluble group is a group obtained by substituting an acetal group, the chemically amplified resist described in <2> Composition .
<4 >
Before SL resin (C) is a resin having a repeating unit represented by the following general formula (A), a chemical amplification type resist composition according to <2>.

In the formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents an alkylene group or an aromatic ring group. R ₀₃ is an alkylene group, and may combine with the Ar ₁ as an aromatic ring group to form a ring together with the —C—C— chain.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.
< 5 >
The chemically amplified resist composition according to < 4 >, wherein the group capable of leaving by the action of an acid as Y in the general formula (A) has a structure represented by the following general formula (B).

In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group, a cycloaliphatic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. In addition, these cycloaliphatic groups and aromatic ring groups may contain a hetero atom.
In addition, at least two of Q, M, and L ₁ may be bonded to each other to form a 5-membered or 6-membered ring .
< 6>
Any of the above < 2 > to < 5>, wherein the resin (C) having a group capable of decomposing by the action of an acid to generate an alkali-soluble group has a repeating unit represented by the following general formula (2) 2. The chemically amplified resist composition according to item 1.

In the general formula (2), R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring.
<7>
(A) A compound represented by the following general formula (I), (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (D) a negative pattern forming material containing a crosslinking agent. Chemically amplified resist composition.

In the general formula (I), each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group.
<8>
The chemical amplification resist composition according to <7>, wherein the crosslinking agent (D) is a compound having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule.
<9>
(E) The chemically amplified resist composition according to <7> or <8>, further containing a compound having a phenolic hydroxyl group.
<10>
The chemical amplification resist composition according to <9>, wherein the compound (E) having the phenolic hydroxyl group is a polymer compound having a repeating unit represented by the following general formula (2).

In the general formula (2), R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring.
<11>
The chemically amplified resist composition according to any one of the above items <1> to <10>, which is for electron beam or extreme ultraviolet exposure.
<12>
The chemical amplification type according to any one of <1> to <11>, wherein the compound (B) is a compound that generates an acid having a volume of 200 ³ or more upon irradiation with actinic rays or radiation. Resist composition.
<13>
A resist film formed from the chemically amplified resist composition according to any one of <1> to <12> above.
<14>
Resist-coated mask blanks coated with the resist film according to <13> above.
<15>
A method for forming a resist pattern, comprising exposing the resist film according to <13> and developing the exposed film.
<16>
The resist pattern formation method including exposing the resist application mask blank as described in said <14>, and developing the said exposed mask blank.
<17>
The manufacturing method of an electronic device containing the resist pattern formation method as described in said <15>.
In addition, although this invention is invention which concerns on said <1>-<17>, below, it described for reference also.

[1]
(A) A chemically amplified resist composition containing a compound represented by the following general formula (I) and (B) a compound that generates an acid upon irradiation with actinic rays or radiation.

In the general formula (I), each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group.
[2]
(C) The chemically amplified resist composition according to [1], further containing a resin having a group that decomposes by the action of an acid to generate an alkali-soluble group, and is for forming a positive type pattern.
[3]
The chemically amplified resist composition according to [2], wherein the resin (C) having a group capable of decomposing by the action of an acid to generate an alkali-soluble group has a repeating unit represented by the following general formula (2): object.

In the general formula (2), R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring.
[4]
(D) The chemically amplified resist composition according to [1], which further contains a crosslinking agent and is for forming a negative pattern.
[5]
The chemically amplified resist composition according to [4], wherein the crosslinking agent (D) is a compound having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule.
[6]
(E) The chemically amplified resist composition according to [1], [4] or [5], which further contains a compound having a phenolic hydroxyl group and is for forming a negative pattern.
[7]
The chemically amplified resist composition according to [6], wherein the compound (E) having a phenolic hydroxyl group is a polymer compound having a repeating unit represented by the following general formula (2).

In the general formula (2), R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring.
[8]
The chemical amplification resist composition according to any one of [1] to [7], wherein the compound (A) is a compound that generates an acid having a volume of 200 ³ or more.
[9]
The chemically amplified resist composition according to any one of [1] to [8], which is for electron beam or extreme ultraviolet exposure.
[10]
The chemical amplification resist according to any one of [1] to [9], wherein the compound (B) is a compound that generates an acid having a volume of 200 ³ or more upon irradiation with actinic rays or radiation. Composition.
[11]
A resist film formed from the chemically amplified resist composition according to any one of [1] to [10].
[12]
[11] Resist-coated mask blanks coated with the resist film according to [11].
[13]
[11] A method for forming a resist pattern, comprising exposing the resist film according to [11] and developing the exposed film.
[14]
[12] A resist pattern forming method comprising exposing the resist-coated mask blank according to [12] and developing the exposed mask blank.
[15]
[12] A photomask obtained by exposing and developing the resist-coated mask blank according to [12].
[16]
The compound represented by the following general formula (IV).

In the general formula, each of R _{4 to} R ₆ represents a hydrogen atom, an alkyl group, or an aryl group.
X represents an alkyl group, a cycloalkyl group, a halogen atom, an aryl group, or an acyl group. m represents an integer of 0 to 5.
[17]
The manufacturing method of an electronic device containing the resist pattern formation method as described in [13].
[18]
[17] An electronic device manufactured by the method for manufacturing an electronic device according to [17].

The present invention preferably further has the following configuration.
[19]
The chemically amplified resist composition according to any one of [1] to [10], wherein R ₁ and R ₂ in the general formula (I) are hydrogen atoms.
[20]
The chemical amplification type according to any one of [1] to [10] and [19], wherein each of R _{4 to} R ₆ in the general formula (I) is an alkyl group, a cycloalkyl group, or an aryl group. Resist composition.
[21]
The monovalent organic group A in the general formula (I) is a residue of a sulfonic acid represented by the formula A-SO ₃ H, and the sulfonic acid is a compound represented by the following general formula (II). [1] to [10], [19] and [20].

In the general formula (II),
Ar ₂ represents an aromatic ring, and may further have a substituent in addition to the sulfonic acid group and the — (D—B) group.
n represents an integer of 0 or more.
D represents a single bond or a divalent linking group.
B represents a hydrocarbon group.
When n is 2 or more, a plurality of — (D—B) groups may be the same or different.
[22]
The chemistry according to [2] or [3], wherein the resin (C) having a group capable of decomposing by the action of an acid to generate an alkali-soluble group is a resin having a repeating unit represented by the following general formula (A): Amplified resist composition.

In the formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
Ar ₁ represents an alkylene group or an aromatic ring group. Note that R ₀₃ is an alkylene group, and may combine with the Ar ₁ as an aromatic ring group to form a ring together with the —C—C— chain. R ₀₃ and Ar ₁ are alkylene groups, and they may be bonded to each other to form, for example, a 5-membered or 6-membered ring together with the —C—C— chain.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.
[23]
The resist pattern forming method according to [13] or [14], wherein the exposure is performed using an electron beam or extreme ultraviolet rays.

According to the present invention, high sensitivity and high resolution (for example, high resolution, excellent pattern shape, small line edge roughness (LER)), high aging stability, low occurrence of scum and good dry etching resistance are satisfied at the same time. It is possible to provide a chemically amplified resist composition capable of forming a pattern to be formed. In particular, since the acid proliferating agent represented by the general formula (I) has an ester group, the balance between sensitivity and stability over time is good, and when the acid proliferating agent undergoes acid decomposition, carboxylic acid is generated A chemically amplified resist composition that is particularly excellent in improving sensitivity can be provided.
Further, according to the present invention, a resist film, a resist coating mask blank, a resist pattern forming method, and a photomask using the chemically amplified resist composition can be provided.

In the description of a group (atomic group) in this specification, the description that does not indicate substitution or non-substitution includes not only a substituent but also a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present invention, “the volume of the acid” means the volume of the region occupied by the van der Waals sphere based on the van der Waals radius of the atoms constituting the acid. Specifically, the “acid volume” is a volume calculated as follows. That is, first, the most stable conformation of the acid is determined by molecular force field calculation using the MM3 method. Thereafter, the van der Waals volume is calculated for this most stable conformation by molecular orbital calculation using the PM3 method. The van der Waals volume is defined as “acid volume”.
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, “light” means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays and EUV light, but also drawing with electron beams and ion beams. Are also included in the exposure.

  The chemically amplified resist composition of the present invention contains (A) a compound represented by the following general formula (I) and (B) a compound that generates an acid upon irradiation with actinic rays or radiation.

In the general formula (I), each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group.

  The structure of the 1,3-diol derivative represented by the general formula (I) (that is, a compound having a structure in which a sulfonyloxy group and an acyloxy group are linked via three carbon atoms) is a sulfonic acid by the action of an acid. (Hereinafter also referred to as an acid proliferating agent). Although the mechanism is not necessarily clear, the present inventors believe that the reaction proceeds according to the following scheme 1 or 2.

In the above scheme, each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group.
As shown in the above scheme, the structure represented by the general formula (I) generates a carbon-carbon double bond by an acid-catalyzed dehydration reaction. Next, a sulfonic acid is produced while producing an alkene or dialkene.

  On the other hand, conventionally known acid proliferators of 1,2-diol derivatives (that is, acid proliferators having a structure in which a sulfonyloxy group and an acyloxy group are linked via two carbon atoms) are as follows: Although it is known to be decomposed by an estimation mechanism, the reactivity is somewhat insufficient, and the effect of improving the sensitivity is small even when used in a chemically amplified resist composition. In the following scheme, Ra represents a hydrogen atom or a substituent, Rb represents a substituent, and A represents a monovalent organic group.

Moreover, a 1,4-diol derivative (that is, a compound having a structure in which a sulfonyloxy group and an acyloxy group are linked via four carbon atoms) does not function as an acid proliferating agent as shown in the following scheme. Note in the following schemes, each of R ₁ to R ₇ represents a hydrogen atom or a substituent, R ₁ to R ₇ are linked to two or more of them together, they may form a ring, R ₈ represents a substituent, and A represents a monovalent organic group.

  The present inventors have found that an acid proliferating agent having a structure represented by the general formula (I) has higher acid proliferating ability and stability over time than a conventional acid proliferating agent. The reason for this is not always clear, but the present inventors speculate as follows. That is, it is presumed that the excellent acid growth ability is caused by the ease of the elimination reaction described above. Moreover, it is estimated that the excellent stability over time is due to the high thermal stability of the structure containing an acyloxy group.

  Therefore, when this acid proliferating agent is used for a chemically amplified resist composition, a composition excellent in both sensitivity and stability over time can be obtained. In addition, when this acid proliferating agent is used, the acid generation contrast is increased, so that the resolution such as LER is improved. Further, since the acid generation contrast is increased, the curability of the resist film in the exposed portion is improved, and as a result, the dry etching resistance is improved. Further, due to the high acid generation contrast between the unexposed portion and the exposed portion, the difference in the contrast between the dissolution rate of the unexposed portion and the exposed portion with respect to the developer increases, and the scum is also reduced.

The chemically amplified resist composition according to the present invention is preferably for electron beam or extreme ultraviolet exposure.
The chemically amplified resist composition according to the present invention may be a negative type chemically amplified resist composition for pattern formation or a positive type chemically amplified resist composition for pattern formation.
Hereinafter, each component of the chemically amplified resist composition of the present invention will be described in detail.

[1] (A) Compound Represented by General Formula (I) The chemically amplified resist composition according to the present invention contains (A) a compound represented by the following general formula (I).

In the general formula (I), each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group.

As described above, the composition according to the present invention contains the compound (A) represented by the general formula (I) and the photoacid generator (B). Therefore, when the composition according to the present invention is irradiated with actinic rays or radiation, the photoacid generator (B) generates an acid. And at least a part of the compound (A) represented by the above general formula (I) contained in the above composition is decomposed by the action of the acid generated from the photoacid generator (B), and sulfonic acid Is generated. Furthermore, the other compound (A) represented by the general formula (I) contained in the composition is decomposed by the action of the generated sulfonic acid. Thereby, the other compound (A) represented by the general formula (I) further generates sulfonic acid.
Thus, the compound (A) represented by the general formula (I) according to the present invention has a function as an acid proliferating agent capable of generating an acid in a chain manner.
Hereinafter, the structure represented by the general formula (I) will be described in detail.

Each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. R ₆ represents a substituent.
Examples of the substituent for R _{1 to} R ₆ include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an alkanoyl group, an alkoxycarbonyl group, Examples include aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylsulfonyl group, arylsulfonyl group, cyano group, alkylthio group, arylthio group and heterocyclic group.

Each of R ₁ and R ₂ is preferably a hydrogen atom, an alkyl group or an alkoxy group, and most preferably a hydrogen atom.
R ₃ is preferably a hydrogen atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom or an alkyl group, and most preferably a hydrogen atom.
Each of R ₄ and R ₅ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a cyano group, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, It is more preferably an atom, an alkyl group or an aryl group, and most preferably an alkyl group or an aryl group. R ₄ and R ₅ are preferably bonded to each other to form a ring, and more preferably an aliphatic hydrocarbon ring having 5 to 7 carbon atoms.
R ₆ is preferably an alkyl group, aryl group, alkenyl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylthio group or arylthio group.

  As the alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an ocdadecyl group, an isopropyl group, and an isobutyl group. , Sec-butyl group, t-butyl group, 1-ethylpentyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl Group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphena A sil group and a 3-nitrophenacyl group are mentioned.

  The cycloalkyl group may have a single ring or may have multiple rings. As the cycloalkyl group having a single ring, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like are preferable. As the polycyclic cycloalkyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, and the like are preferable. A cycloalkyl group having 3 to 8 carbon atoms is preferred, and for example, a cyclopentyl group and a cyclohexyl group are more preferred.

  As an alkenyl group, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group, etc. are mentioned.

  The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The aryl group is preferably an aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, 5 -Naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-cumenyl Group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group , Biantracenyl group, teranthracenyl group, quarter N-thracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group , Rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group, and oberenyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a trifluoromethoxy group, a hexyloxy group, a t-butoxy group, a 2-ethylhexyloxy group, a cyclohexyloxy group, a decyloxy group, and a dodecyloxy group. Is mentioned.

  Examples of the aryloxy group include phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, tolyloxy group, methoxyphenyloxy group, naphthyloxy group, chlorophenyloxy group, trifluoromethylphenyloxy group, and cyanophenyloxy. Groups and nitrophenyloxy groups.

  The alkanoyl group is preferably an alkanoyl group having 2 to 20 carbon atoms. For example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4 -Methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl group, 2-butoxybenzoyl group, Examples include 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group and 4-methoxybenzoyl group.

  The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group. , Octadecyloxycarbonyl group and trifluoromethyloxycarbonyl group.

  Examples of the aryloxycarbonyl group include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyl. Oxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyl Alkoxycarbonyl group, 4-cyanophenyl oxycarbonyl group and a 4-methoxyphenyl oxycarbonyl group.

  Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a butylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, a decylcarbonyloxy group, an octadecylcarbonyloxy group, and a tricarbonyl group. A fluoromethylcarbonyloxy group is mentioned.

  Examples of the arylcarbonyloxy group include a phenylcarbonyloxy group, a 1-naphthylcarbonyloxy group, a 2-naphthylcarbonyloxy group, a 4-methylsulfanylphenylcarbonyloxy group, a 4-phenylsulfanylphenylcarbonyloxy group, and 4-dimethylamino. Phenylcarbonyloxy group, 4-diethylaminophenylcarbonyloxy group, 2-chlorophenylcarbonyloxy group, 2-methylphenylcarbonyloxy group, 2-methoxyphenylcarbonyloxy group, 2-butoxyphenylcarbonyloxy group, 3-chlorophenylcarbonyloxy group 3-trifluoromethylphenylcarbonyloxy group, 3-cyanophenylcarbonyloxy group, 3-nitrophenylcarbonyloxy group, 4-fluorophenyl Ylcarbonyl group, 4-cyanophenyl carbonyl group and a 4-methoxyphenyl carbonyloxy group.

  As the alkylsulfonyloxy group, an alkylsulfonyloxy group having 1 to 20 carbon atoms is preferable. For example, a methylsulfonyloxy group, an ethylsulfonyloxy group, a propylsulfonyloxy group, an isopropylsulfonyloxy group, a butylsulfonyloxy group, a hexylsulfonyloxy group. Group, cyclohexylsulfonyloxy group, octylsulfonyloxy group, 2-ethylhexylsulfonyloxy group, decanoylsulfonyloxy group, dodecanoylsulfonyloxy group, octadecanoylsulfonyloxy group, cyanomethylsulfonyloxy group, methoxymethylsulfonyloxy group and A perfluoroalkylsulfonyloxy group may be mentioned.

  The arylsulfonyloxy group is preferably an arylsulfonyloxy group having 6 to 30 carbon atoms. For example, a phenylsulfonyloxy group, a 1-naphthylsulfonyloxy group, a 2-naphthylsulfonyloxy group, a 2-chlorophenylsulfonyloxy group, 2- Methylphenylsulfonyloxy group, 2-methoxyphenylsulfonyloxy group, 2-butoxyphenylsulfonyloxy group, 3-chlorophenylsulfonyloxy group, 3-trifluoromethylphenylsulfonyloxy group, 3-cyanophenylsulfonyloxy group, 3-nitro Phenylsulfonyloxy group, 4-fluorophenylsulfonyloxy group, 4-cyanophenylsulfonyloxy group, 4-methoxyphenylsulfonyloxy group, 4-methylsulfanylphenylsulfonate Oxy group, and a 4-phenylsulfanyl-phenyl sulfonyloxy group and a 4-dimethylaminophenyl sulfonyloxy group.

  As the alkylsulfonyl group, an alkylsulfonyl group having 1 to 20 carbon atoms is preferable. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group, an octylsulfonyl group. Group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and perfluoroalkylsulfonyl group.

  The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2 -Methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4 -Cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group and 4-dimethylaminophenylsulfonyl group It is.

  Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, n-butylthio group, trifluoromethylthio group, hexylthio group, t-butylthio group, 2-ethylhexylthio group, cyclohexylthio group, decylthio group, and dodecylthio group. Can be mentioned.

  Examples of the arylthio group include phenylthio group, 1-naphthylthio group, 2-naphthylthio group, tolylthio group, methoxyphenylthio group, naphthylthio group, chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, and nitrophenylthio group. Groups.

  The heterocyclic group is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Examples of this heterocyclic group include a thienyl group, a benzo [b] thienyl group, a naphtho [2,3-b] thienyl group, a thiantenyl group, a furyl group, a pyranyl group, an isobenzofuranyl group, a chromenyl group, and a xanthenyl group. Phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl Group, prynyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridine Le group, Acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, phenalsadinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolidinyl Group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group and thioxanthryl group.

The group of R _{1 to} R ₅ may further have a substituent. Examples of the substituent that the group may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; Group, ethoxy group and alkoxy group such as tert-butoxy group; aryloxy group such as phenoxy group and p-tolyloxy group; alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acetoxy group, propionyloxy group And acyloxy groups such as benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; phenylsulfanyl group and p-to Arylsulfanyl groups such as sulfanyl group; alkylamino groups such as methylamino group and cyclohexylamino group; dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group; phenylamino group and p-tolylamino group Arylamino group; alkyl group such as methyl group, ethyl group, tert-butyl group and dodecyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group and cycloheptyl group; phenyl group, p-tolyl group, xylyl group, cumenyl group , Naphthyl group, anthryl group and phenanthryl group; hydroxyl group; carboxy group; formyl group; mercapto group; sulfo group; mesyl group; p-toluenesulfonyl group; amino group; nitro group; cyano group; Group; Romechiru group; a trimethylsilyl group; phosphinico group; phosphono group; trimethyl ammonium Niu mill group; dimethylsulfoxide Niu mill group, as well as triphenyl phenacyl phosphonium Niu mill group.

As described above, two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. This ring may be an aliphatic or aromatic hydrocarbon ring or a heterocyclic ring containing a hetero atom. Moreover, these R < ₁ > -R < ₅ > may form the condensed ring.

  Examples of the aliphatic or aromatic hydrocarbon ring include 5-membered ring, 6-membered ring and 7-membered ring. The hydrocarbon ring is preferably a 5-membered or 6-membered ring, particularly preferably a 5-membered ring.

  Examples of the heterocyclic ring include those containing a sulfur atom, oxygen atom or nitrogen atom as a hetero atom. As this heterocyclic ring, those containing a sulfur atom as a hetero atom are more preferred.

  As a condensed ring, the condensed ring which consists only of hydrocarbon rings is mentioned, for example. Examples of the polycyclic fused ring include those in which 2 to 4 benzene rings form a condensed ring and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.

  The condensed ring may be a condensed ring containing at least one heterocyclic ring. Examples of this condensed ring include those in which a benzene ring and a 5-membered heterocyclic ring form a condensed ring, and those in which a benzene ring and a 6-membered heterocyclic ring form a condensed ring.

Examples of the ring that R _{1 to} R ₅ can form include, for example, cycloheptane ring, cyclohexane ring, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan Ring, thiophene ring, dithiolane ring, oxirane, dioxirane ring, thiirane ring, pyrrolidine ring, piperidine ring, imidazole ring, isoxazole ring, benzodithiol ring, oxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring, benzoxazole ring Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, benzodithiol ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, Fuchirijin ring, quinoxaline ring, quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, include phenothiazine ring and a phenazine ring. Among these, a cycloheptane ring, a cyclohexane ring, a dithiolane ring, a benzodithiol ring, a benzothiazole ring, a benzimidazole ring, and a benzoxazole ring are particularly preferable.

As R < ₁ > -R < ₆ > in general formula (I), what is described in the following chemical formula is mentioned, for example. In addition, A in the following chemical formula is synonymous with A in the said general formula (I).

  A represents a monovalent organic group. Although it does not specifically limit as a monovalent organic group, It is preferable that A is an alkyl group, a cycloalkyl group, or an aromatic group. Each of these alkyl groups, cycloalkyl groups, and aromatic groups may have a substituent.

As an alkyl group, a C1-C30 alkyl group is preferable, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group , Tetradecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.
The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. Can be mentioned. Of these, a polycyclic cycloalkyl group is preferred and an adamantyl group is most preferred from the viewpoint of achieving both improved roughness and higher sensitivity.

  Examples of the aromatic group include a benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzo Thiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Ntoren ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. Of these, a benzene ring, a naphthalene ring or an anthracene ring is preferable, and a benzene ring is more preferable, from the viewpoint of achieving both roughness improvement and high sensitivity.

  Examples of substituents that the alkyl group, cycloalkyl group and aromatic group may have include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group and tert-butoxy group Aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group , Acyl groups such as benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; phenylsulfanyl group and p-tolylsulfanyl Arylsulfanyl groups such as; alkyl groups such as methyl, ethyl, tert-butyl, and dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl; phenyl, p-tolyl, Aryl group such as xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxy group; carboxy group; formyl group; sulfonyl group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; Amino group; thioxy group; or a combination thereof.

A preferably has a ring structure. Table A, more preferably, a residue of a sulfonic acid represented by the formula A-SO ₃ H, the following formula sulfonic acid represented by the formula A-SO ₃ H by (II) or (III) It is a compound. More preferably, acid A-SO ₃ H is a compound represented by the following general formula (II).

In formula (II),
Ar ₂ represents an aromatic ring, and may further have a substituent in addition to the sulfonic acid group and the — (D—B) group.
n represents an integer of 0 or more. n is preferably an integer of 1 or more, more preferably an integer of 1 to 4, still more preferably 2 or 3, and most preferably 3.
D represents a single bond or a divalent linking group. The divalent linking group is an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, or an ester group.
B represents a hydrocarbon group.
When n is 2 or more, a plurality of — (D—B) groups may be the same or different.

In formula (III),
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² in the case where a plurality of R ¹ and R ^{2 are present.} May be the same or different.
L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same or different.
E represents a group having a ring structure.
x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10.

First, the sulfonic acid represented by the formula (II) will be described in detail.
In formula (II), Ar ₂ is preferably an aromatic ring having 6 to 30 carbon atoms.
Specifically, the aromatic ring represented by Ar ₂ is, for example, a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indecene ring, a perylene ring, a pentacene ring, an acetaphthalene ring, or a phenanthrene ring. , Anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, India Lysine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, A phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, or a phenazine ring. Of these, a benzene ring, a naphthalene ring or an anthracene ring is preferable, and a benzene ring is more preferable, from the viewpoint of achieving both roughness improvement and high sensitivity.

When Ar ₂ further has a substituent other than the sulfonic acid group and the — (D—B) group, examples of the substituent include the following. That is, as this substituent, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group Alkylthioxy groups such as methylthioxy, ethylthioxy and tert-butylthioxy groups; arylthioxy groups such as phenylthioxy and p-tolylthioxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl Acetoxy group; linear alkyl group and branched alkyl group such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; vinyl group, propenyl group and hexenyl group, etc. An alkenyl group; Styrene group; hydroxy group; a carboxy group; an aryl group such as a phenyl group and tolyl group; an alkynyl group such as propynyl group and hexynyl group are exemplified as well as sulfonic acid group; a mercapto group. Of these, straight chain alkyl groups and branched alkyl groups are preferred from the viewpoint of improving roughness.

  In the formula (II), D is preferably a single bond, or an ether group or an ester group. More preferably, D is a single bond.

  In formula (II), B is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a cycloalkyl group. B is preferably an alkyl group or a cycloalkyl group. The alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B may have a substituent.

  The alkyl group as B is preferably a branched alkyl group. Examples of this branched alkyl group include isopropyl group, tert-butyl group, tert-pentyl group, neopentyl group, sec-butyl group, isobutyl group, isohexyl group, 3,3-dimethylpentyl group and 2-ethylhexyl group. It is done.

  The cycloalkyl group as B may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. Can be mentioned.

  The alkenyl group as B is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

  The alkynyl group as B is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The aryl group as B is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

  When the alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B has a substituent, examples of the substituent include the following. That is, as this substituent, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group Alkylthioxy groups such as methylthioxy, ethylthioxy and tert-butylthioxy groups; arylthioxy groups such as phenylthioxy and p-tolylthioxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl Acetoxy group; straight chain alkyl group such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; branched alkyl group; cycloalkyl group such as cyclohexyl group; vinyl group; , Propenyl And alkenyl groups such as hexenyl groups; acetylene group; hydroxy group; a carboxy group; a sulfonic group; an aryl group such as a phenyl group and tolyl group; an alkynyl group such as propynyl group and hexynyl group and a carbonyl group. Among these, a straight chain alkyl group and a branched alkyl group are preferable from the viewpoint of achieving both improvement in roughness and high sensitivity.

Next, the sulfonic acid represented by the formula (III) will be described in detail.
In formula (III), Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. As this alkyl group, a C1-C10 thing is preferable and a C1-C4 thing is more preferable. The alkyl group substituted with a fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F _{17, CH 2 CF 3, CH} 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F ₉ or CH ₂ CH ₂ C ₄ F ₉ . Among these, a fluorine atom or CF ₃ is preferable, and a fluorine atom is most preferable.

In formula (III), each of R ¹ and R ² is a group selected from a hydrogen atom, a fluorine atom, an alkyl group, and an alkyl group substituted with at least one fluorine atom. The alkyl group which may be substituted with a fluorine atom is preferably an alkyl group having 1 to 4 carbon atoms. Moreover, as an alkyl group substituted by the fluorine atom, a C1-C4 perfluoroalkyl group is especially preferable. Specifically, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH _{2 CH 2 CF 3, CH 2 C} 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 or _CH 2 _CH 2 _{C 4} F ₉ is mentioned, and among them, CF ₃ is preferable.

In the formula (III), x is preferably an integer of 1 to 8, and more preferably an integer of 1 to 4. y is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and still more preferably 0. z is preferably an integer of 0 to 8, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 3.
In formula (III), L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -OCO-, -CONR- (R is a hydrogen atom, an alkyl group or a cycloalkyl group), -NR- (R is a hydrogen atom, an alkyl group or a cycloalkyl group). ), - CO -, - O -, - S -, - SO -, - SO 2 -, an alkylene group, cycloalkylene group, alkenylene group and linking groups such as a plurality of these are combined and the like. Among them, -COO -, - OCO -, - CONR -, - CO -, - O -, - S -, - SO- or -SO ₂ - are preferred, -COO -, - OCO- or -SO ₂ - is More preferred.

  In formula (III), E represents a group having a ring structure. Examples of E include a cyclic aliphatic group, an aryl group, and a group having a heterocyclic structure.

  The cycloaliphatic group as E may have a monocyclic structure or a polycyclic structure. As the cyclic aliphatic group having a monocyclic structure, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable. The cycloaliphatic group having a polycyclic structure is preferably a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. In particular, when a cycloaliphatic group having a bulky structure of 6-membered ring or more is adopted as E, diffusibility in the film in the PEB (post-exposure heating) step is suppressed, and the resolution and EL (exposure latitude) are further improved. It becomes possible to improve.

  The aryl group as E is, for example, a benzene ring, naphthalene ring, phenanthrene ring or anthracene ring.

  The group having a heterocyclic structure as E may have aromaticity or may not have aromaticity. The heteroatom contained in this group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a decahydroquinoline ring, a pyridine ring, a piperidine ring, and a morpholine ring. Among these, a furan ring, a thiophene ring, a decahydroquinoline ring, a pyridine ring, a piperidine ring, and a morpholine ring are preferable.

  E may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), a cycloalkyl group (preferably 3 to 12 carbon atoms), an aryl group (carbon number). 6-14 are preferred), hydroxy group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group and sulfonic acid ester group.

The sulfonic acid ASO ₃ H generated from the compound (A) represented by the general formula (I) only suppresses the diffusion of the acid generated by exposure to the non-exposed portion and improves the resolution and pattern shape. From the viewpoint of improving the stability over time, the volume is preferably large. Specifically, the compound (A) represented by the general formula (I) is preferably a compound that generates an acid having a volume of 200 ³ or more (more preferably sulfonic acid), and a volume of 240 ³ or more. More preferably, the compound generates an acid (more preferably sulfonic acid) having a size of 270 to ³ or more, and still more preferably is a compound that generates an acid having a volume of 270 to ³ or more (more preferably sulfonic acid). (more preferably sulfonic acid) acid volume 300 Å ³ or more dimensions, especially preferably a compound which generates an (more preferably sulfonic acid) acid volume 400 Å ³ or more dimensions are compounds capable of generating an Particularly preferred. However, from the viewpoint of sensitivity and coating solvent solubility, the volume is preferably 2000 ³ or less, and more preferably 1500 ³ or less. Examples of the volume of sulfonic acid ASO ₃ H are given below together with the structure of sulfonic acid generated from the acid proliferating agent represented by the general formula (I).
Each of these examples is accompanied by a calculated volume value.
This value was obtained as follows using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example was input. Next, using this structure as an initial structure, the most stable conformation of each acid was determined by molecular force field calculation using the MM3 method. Thereafter, molecular orbital calculation using the PM3 method was performed for these most stable conformations to calculate “accessible volume” of each acid.
The acid proliferating agent represented by the general formula (I) according to the present invention is not limited to the compounds generating sulfonic acid described below.

The compound (A) represented by the general formula (I) is preferably a compound represented by the following general formula (IV).
The present invention also relates to a compound represented by the following general formula (IV).

In the general formula, each of R _{4 to} R ₆ represents a hydrogen atom, an alkyl group, or an aryl group.
X represents an alkyl group, a cycloalkyl group, a halogen atom, an aryl group, or an acyl group. m represents an integer of 0 to 5.
The alkyl group and aryl group for R _{4 to} R ₆ may have a substituent. Specific examples and preferred examples of the alkyl group and aryl group include those described above for R _{1 to} R ₆ in formula (I). And the same alkyl group and aryl group as described above.
The alkyl group, cycloalkyl group, aryl group and acyl group for X may have a substituent.
Specific examples and preferred examples of the alkyl group, cycloalkyl group, halogen atom, aryl group, and acyl group for X include alkyl groups, cycloalkyl groups, and halogen atoms described above as R _{1 to} R ₆ in formula (I). , Aryl groups, and acyl groups.
m is preferably an integer of 1 to 3.

The compounds represented by the general formula (I) or (IV) can be used singly or in combination of two or more.
The content of the compound represented by the general formula (I) or (IV) is preferably 0.1 to 40% by mass, more preferably 0.5 to 0.5% based on the total solid content of the composition. It is 30 mass%, More preferably, it is 1.0-20 mass%.

  As a method for producing the compound (A) represented by the general formula (I) of the present invention, a corresponding diol compound and a sulfonyl halide or a sulfonic acid anhydride are used in the presence of a base (for example, triethylamine or pyridine). By reacting in an inert solvent such as THF, DMF and acetonitrile, or a basic solvent such as pyridine, a compound in which one hydroxyl group of the diol is sulfonylated can be synthesized. As reaction temperature, -10-60 degreeC is preferable. Next, using the compound and an acid halide or acid anhydride, an acid catalyst (for example, cerium trifluoromethanesulfonate, cobalt chloride, etc.) or in the presence of a base (for example, triethylamine, pyridine, dimethylaminopyridine, diisopropylethylamine) And butyl lithium, an inorganic base, etc.) in an inert solvent such as THF, DMF and acetonitrile, the target compound (A) represented by the general formula (I) can be synthesized. As reaction temperature, -10-60 degreeC is preferable.

  Further, by using alkylsulfonyl halide and arylsulfonyl halide as the sulfonyl halide and using acyl halide and arylcarbonyl halide as the acid halide, various corresponding sulfonic acid generating compounds can be synthesized.

[2] (B) Compound that generates an acid upon irradiation with actinic rays or radiation The chemically amplified resist composition of the present invention comprises a compound (B) that generates an acid upon irradiation with an actinic ray or radiation (hereinafter referred to as appropriate). The compound is abbreviated as “acid generator”).
Preferred forms of the acid generator include onium compounds. Examples of such onium compounds include sulfonium salts, iodonium salts, phosphonium salts, and the like.
Another preferred form of the acid generator includes a compound that generates sulfonic acid, imide acid, or methide acid upon irradiation with actinic rays or radiation. Examples of the acid generator in the form include a sulfonium salt, an iodonium salt, a phosphonium salt, an oxime sulfonate, and an imide sulfonate.

  The acid generator is preferably a compound that generates an acid upon irradiation with an electron beam or extreme ultraviolet rays.

  In the present invention, preferred onium compounds include sulfonium compounds represented by the following general formula (5) or iodonium compounds represented by the general formula (6).

In general formulas (5) and (6),
R _a1 , R _a2 , R _a3 , R _a4 and R _a5 each independently represent an organic group.
X ⁻ represents an organic anion.
Hereinafter, the sulfonium compound represented by the general formula (5) and the iodonium compound represented by the general formula (6) will be described in more detail.

R _{a1 to} R _a3 in the general formula (5) and R _a4 and R _{a5 in} the general formula (6) each independently represent an organic group, preferably at least one of R _{a1 to} R _a3 , In addition, at least one of R _a4 and R _{a5 is} an aryl group. As the aryl group, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
X in the general formula (5) and (6) ^- organic anions are, for example, sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, and the like, preferably, below An organic anion represented by the general formula (7), (8) or (9), more preferably an organic anion represented by the following general formula (7).

In the general formulas (7), (8) and (9), Rc ₁ , Rc ₂ , Rc ₃ and Rc ₄ each represents an organic group.

The organic anion of X ⁻ corresponds to sulfonic acid, imide acid, methide acid, etc., which are acids generated by irradiation with actinic rays or radiation such as electron beams and extreme ultraviolet rays.
Examples of the organic group of R _{c1 to} R _c4 include an alkyl group, a cycloalkyl group, an aryl group, or a group in which a plurality of these are connected. More preferably among these organic groups, the alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, a cycloalkyl group substituted with a fluorine atom or a fluoroalkyl group, a phenyl group substituted with a fluorine atom or a fluoroalkyl group It is. A plurality of the organic groups of R _{c2 to} R _c4 may be connected to each other to form a ring, and the group to which the plurality of organic groups are connected includes an alkylene group substituted with a fluorine atom or a fluoroalkyl group Is preferred. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. However, the terminal group preferably does not contain a fluorine atom as a substituent.

In the present invention, the compound (B) that generates an acid has a volume of 130 to ³ or more from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution and pattern shape. It is preferable that the compound generates an acid (more preferably sulfonic acid) having a size of 200, and more preferably a compound that generates an acid having a volume of 200 ³ or more (more preferably sulfonic acid). More preferably, the compound generates an acid having a size of 240 大 き³ or more (more preferably sulfonic acid), and a compound generating an acid having a volume of 400 体積³ or more (more preferably sulfonic acid). Is particularly preferred. However, from the viewpoint of sensitivity and coating solvent solubility, the volume is preferably 2000 ³ or less, and more preferably 1500 ³ or less.
The volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
In the present invention, particularly preferred acid generators are exemplified below. In addition, the calculated value of the volume is appended to a part of the example (unit ^{３ 3} ). In addition, the calculated value calculated | required here is a volume value of the acid which the proton couple | bonded with the anion part.

The content of the acid generator (B) in the composition is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, based on the total solid content of the resist composition. More preferably, it is 1 to 18% by mass.
An acid generator can be used individually by 1 type or in combination of 2 or more types.

[3] (C) Resin having a group (hereinafter also referred to as an acid-decomposable group) that decomposes by the action of an acid to generate an alkali-soluble group The chemical amplification resist composition of the present invention forms a positive pattern. Sometimes, it is preferable to contain a resin (C) having an acid-decomposable group.
This resin may have an acid-decomposable group in one of the main chain and side chain of the resin, or in both of them. This resin preferably has an acid-decomposable group in the side chain. Moreover, it is preferable that resin (C) has a repeating unit which has an acid-decomposable group.

  As the acid-decomposable group, a group in which a hydrogen atom of an alkali-soluble group such as a —COOH group and a —OH group is substituted with a group capable of leaving by the action of an acid is preferable. As the group capable of leaving by the action of an acid, an acetal group or a tertiary ester group is particularly preferable.

  Examples of the base resin in the case where these acid-decomposable groups are bonded as side chains include alkali-soluble resins having —OH or —COOH groups in the side chains. Examples of such alkali-soluble resins include those described later.

  The alkali dissolution rate of these alkali-soluble resins is preferably 17 nm / second or more as measured with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution (23 ° C.). This speed is particularly preferably 33 nm / second or more.

  From this point of view, particularly preferable alkali-soluble resins include o-, m- and p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene). ), Partially O-alkylated or O-acylated product of poly (hydroxystyrene), styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, and hydrogenated novolac resin. And a resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid and norbornenecarboxylic acid.

  Examples of the preferred repeating unit having an acid-decomposable group include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, and (meth) acrylic acid tertiary alkyl ester. As this repeating unit, 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate is more preferable.

  Resins that are decomposed by the action of an acid and have increased solubility in an alkaline developer are disclosed in European Patent 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. As disclosed, for example, a resin is reacted with a precursor of a group capable of leaving by the action of an acid, or an alkali-soluble resin monomer having a group capable of leaving by the action of an acid is combined with various monomers. It is obtained by polymerizing.

  In the case where the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray or high energy light having a wavelength of 50 nm or less (for example, EUV), this resin preferably has a hydroxystyrene repeating unit. . More preferably, the resin is a copolymer of hydroxystyrene and hydroxystyrene protected with a group capable of leaving by the action of an acid, or a copolymer of hydroxystyrene and a (meth) acrylic acid tertiary alkyl ester. It is.

  Specific examples of such a resin include a resin having a repeating unit represented by the following general formula (A).

In the formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents an alkylene group or an aromatic ring group. Note that R ₀₃ is an alkylene group, and may combine with the Ar ₁ as an aromatic ring group to form a ring together with the —C—C— chain. R ₀₃ and Ar ₁ are alkylene groups, and they may be bonded to each other to form, for example, a 5-membered or 6-membered ring together with the —C—C— chain.

n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4, preferably 1 to 2, and more preferably 1.

The alkyl group as R _{01 to} R ₀₃ is, for example, an alkyl group having 20 or less carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a hexyl group. , 2-ethylhexyl group, octyl group or dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. In addition, these alkyl groups may have a substituent.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R _{01 to} R ₀₃ described above.

  The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Preferably, a C3-C8 monocyclic cycloalkyl group, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is mentioned. In addition, these cycloalkyl groups may have a substituent.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.

When R ₀₃ represents an alkylene group, the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.

The aromatic ring group as Ar ₁ preferably has 6 to 14 carbon atoms, and examples thereof include a benzene ring, a toluene ring and a naphthalene ring. In addition, these aromatic ring groups may have a substituent.

Examples of the group Y leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ). _{), - C (R 01)} (R 02) (oR 39), - C (R 01) (R 02) -C (= O) -O-C (R 36) (R 37) (R 38) and And a group represented by —CH (R ₃₆ ) (Ar).

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring structure.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
Ar represents an aryl group.

The alkyl group as R _{36 to} R ₃₉ , R ₀₁ or R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, sec-butyl. Groups, hexyl groups and octyl groups.

The cycloalkyl group as R _{36 to} R ₃₉ , R ₀₁ , or R ₀₂ may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, A tetracyclododecyl group and an androstanyl group are mentioned. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group as R _{36 to} R ₃₉ , R ₀₁ R ₀₂ or Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group as R _{36 to} R ₃₉ , R ₀₁ or R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and for example, a benzyl group, a phenethyl group and a naphthylmethyl group are preferable.
The alkenyl group as R _{36 to} R ₃₉ , R ₀₁ or R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The aryl group as R _{36 to} R ₃₉ , R ₀₁ R ₀₂ or Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group as R _{36 to} R ₃₉ , R ₀₁ or R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and for example, a benzyl group, a phenethyl group and a naphthylmethyl group are preferable.
The alkenyl group as R _{36 to} R ₃₉ , R ₀₁ or R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The ring that R ₃₆ and R ₃₇ may be bonded to each other may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkane structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic type, a cycloalkane structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. Note that some of the carbon atoms in the ring structure may be substituted with a heteroatom such as an oxygen atom.
Each of the above groups may have a substituent. Examples of this substituent include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, and acyloxy groups. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.
A structure in which a plurality of repeating units represented by the general formula (A) are bonded to each other at the group Y leaving by the action of an acid may be used.
As the group Y leaving by the action of an acid, a structure represented by the following general formula (B) is more preferable.

In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group, a cycloaliphatic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. In addition, these cycloaliphatic groups and aromatic ring groups may contain a hetero atom.
In addition, at least two of Q, M, and L ₁ may be bonded to each other to form a 5-membered or 6-membered ring.
The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and An octyl group is mentioned.
The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specifically includes a phenyl group, a tolyl group, a naphthyl group, and an anthryl group.
The aralkyl group as L ₁ and L ₂ is, for example, an aralkyl group having 6 to 20 carbon atoms, and specific examples include a benzyl group and a phenethyl group.
The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group), cycloalkylene group (for example, cyclopentylene group or cyclohexylene group). ), an alkenylene group (e.g., ethenylene group, propenylene group or butenylene group), an arylene group (e.g., phenylene, tolylene or naphthylene group), - S -, - O -, - CO -, - SO 2 -, - N (R ₀ ) — or a combination of two or more thereof. Here, R ₀ is a hydrogen atom or an alkyl group. The alkyl group as R ₀ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. Can be mentioned.

The alkyl group and cycloalkyl group as Q are the same as the above-described groups as L ₁ and L ₂ .
Examples of the cyclic aliphatic group or aromatic ring group as Q include the cycloalkyl group and aryl group as L ₁ and L ₂ described above. These cycloalkyl group and aryl group are preferably groups having 3 to 15 carbon atoms.
Examples of the cycloaliphatic group or aromatic ring group containing a hetero atom as Q include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, And groups having a heterocyclic structure such as thiazole and pyrrolidone. However, the ring is not limited to these as long as it is a ring formed of carbon and a heteroatom, or a ring formed only of a heteroatom.
Examples of the ring structure that can be formed by bonding at least two of Q, M, and L ₁ to each other include a 5-membered or 6-membered ring structure in which these form a propylene group or a butylene group. This 5-membered or 6-membered ring structure contains an oxygen atom.
Each group represented by L ₁ , L ₂ , M and Q in the general formula (2) may have a substituent. Examples of this substituent include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, and acyloxy groups. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.
The group represented by-(MQ) is preferably a group having 1 to 30 carbon atoms, and more preferably a group having 5 to 20 carbon atoms. In particular, from the viewpoint of outgas suppression, a group having 6 or more carbon atoms is preferable.
Specific examples of the repeating unit represented by the general formula (A) are shown below, but are not limited thereto.

The content of the repeating unit represented by the general formula (A) in the resin (C) is preferably in the range of 10 to 90 mol%, more preferably 10 to 70 mol%, based on all repeating units. And particularly preferably within the range of 20 to 60 mol%.
Resin (C) can also have a repeating unit represented by the following general formula (X) as a repeating unit having an acid-decomposable group.

In general formula (X),
Xa ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents a linear or branched alkyl group, or a monocyclic or polycyclic cycloalkyl group. In addition, at least two of Rx _{1 to} Rx ₃ may be bonded to each other to form a monocyclic or polycyclic cycloalkyl group.
Examples of the divalent linking group as T include an alkylene group, a-(COO-Rt)-group, and a-(O-Rt)-group. Here, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a-(COO-Rt)-group. Here, Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, a — (CH ₂ ) ₂ — group, or a — (CH ₂ ) ₃ — group.
The alkyl group as Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. It is.
The cycloalkyl group as Rx _{1 to} Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. It is a polycyclic cycloalkyl group.
The cycloalkyl group that can be formed by combining two of Rx _{1 to} Rx ₃ with each other includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. And a polycyclic cycloalkyl group such as an adamantyl group are preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
In particular, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to each other to form the above-described cycloalkyl group is preferable.
Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.
Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto.

The content of the repeating unit represented by the general formula (X) in the resin is preferably in the range of 3 to 90 mol%, more preferably in the range of 5 to 80 mol% with respect to all the repeating units. And particularly preferably within the range of 7 to 70 mol%.
The content of the group capable of decomposing with an acid is determined by the formula B according to the number of groups (B) capable of decomposing with an acid in the resin and the number of alkali-soluble groups not protected by a group capable of leaving with an acid (S). / (B + S). This content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

  The resin (C) preferably has a repeating unit represented by the following general formula (2).

In General Formula (2), R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring.

R ₁₂ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom for reasons of developability.

The aromatic ring of Ar is a monocyclic or polycyclic aromatic ring, an aromatic hydrocarbon ring having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, or, for example, Aromatic ring heterocycles including heterocycles such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring Can be mentioned. Among these, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable from the viewpoint of sensitivity.
The aromatic ring of Ar may have a substituent other than the group represented by -OH, and examples of the substituent include an alkyl group, a cycloalkyl group, a halogen atom, a hydroxyl group, an alkoxy group, and a carboxyl group. Group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylsulfonyloxy group, and arylcarbonyl group.
The repeating unit represented by the general formula (2) is a repeating unit derived from hydroxystyrene (that is, a repeating unit in which R ₁₂ is a hydrogen atom and Ar is a benzene ring in the general formula (2)). Is preferable from the viewpoint of sensitivity.

  The content of the repeating unit represented by the general formula (2) is preferably 10 to 90 mol%, more preferably 20 to 85 mol%, based on all repeating units of the resin (C). 30 to 85 mol% is more preferable.

  Hereinafter, although the example of the repeating unit represented by General formula (2) is described, it is not limited to this.

When the composition of the present invention is irradiated with ArF excimer laser light, the resin preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure. Hereinafter, such a resin is referred to as “alicyclic hydrocarbon-based acid-decomposable resin”.
As this alicyclic hydrocarbon-based acid-decomposable resin, a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following general formulas (pI) to (pV), and the following general formula (II- A resin containing at least one selected from the group consisting of repeating units represented by AB) is preferred.

In general formulas (pI) to (pV),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group. However, at least one of R _{12 to} R ₁₄ represents a cycloalkyl group. Moreover, any of R ₁₅ and R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Further, any one of R ₁₉ and R ₂₁ represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring structure.

In general formula (II-AB),
R ₁₁ ′ and R ₁₂ ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z ′ represents an atomic group necessary for forming an alicyclic structure with two bonded carbon atoms (C—C).
The general formula (II-AB) is more preferably the following general formula (II-AB1) or general formula (II-AB2).

In general formulas (II-AB1) and (II-AB2),
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, —COOH, —COOR ₅ , a group that decomposes by the action of an acid, —C (═O) —XA ′. —R ₁₇ ′ represents an alkyl group or a cycloalkyl group. Here, R ₅ represents an alkyl group, a cycloalkyl group, or a group having a lactone structure. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A ′ represents a single bond or a divalent linking group. R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or a group having a lactone structure. Here, R ₆ represents an alkyl group or a cycloalkyl group. In addition, at least two of R ₁₃ ′ to R ₁₆ ′ may be bonded to each other to form a ring structure.
n represents 0 or 1.
In general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. , N-butyl group, sec-butyl group and t-butyl group.
The cycloalkyl group in R _{12 to} R ₂₅ or the cycloalkyl group formed by Z and a carbon atom may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Specific examples include groups having a monocyclo, bicyclo, tricyclo, and tetracyclo structure having 5 or more carbon atoms. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable.

Preferred cycloalkyl groups include, for example, adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group. Group, cyclodecanyl group and cyclododecanyl group. More preferably, an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group, and a tricyclodecanyl group are exemplified.
These alkyl groups and cycloalkyl groups may have a substituent. As this substituent, an alkyl group (C1-C4), a halogen atom, a hydroxyl group, an alkoxy group (C1-C4), a carboxyl group, and an alkoxycarbonyl group (C2-C6) are mentioned, for example. These substituents may have further substituents. As this further substituent, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned, for example.
The structures represented by the general formulas (pI) to (pV) can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.
Specifically, for example, a structure in which a hydrogen atom such as a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group is substituted with a structure represented by the general formulas (pI) to (pV) can be given. A structure in which a hydrogen atom of a carboxylic acid group or a sulfonic acid group is substituted with a structure represented by general formulas (pI) to (pV) is preferable.
As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (pI) to (pV), a repeating unit represented by the following general formula (pA) is preferable.

In general formula (pA),
R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. Each of the plurality of Rs may be the same as or different from each other.
A is selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, a urea group, and combinations of two or more thereof, preferably It is a single bond.
Rp ₁ is a group represented by any one of the general formulas (pI) to (pV).
The repeating unit represented by the general formula (pA) is most preferably a repeating unit of 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate.
Specific examples of the repeating unit represented by the general formula (pA) include those similar to those exemplified above as the repeating unit represented by the general formula (X), and are represented by the general formula (pA). Specific examples of other repeating units are shown below.

In the above structural formulas, Rx is _H, represent CH 3, CF ₃ or _CH 2 OH, Rxa and Rxb each independently represents an alkyl group having 1 to 4 carbon atoms.
The halogen atom as R ₁₁ ′ or R ₁₂ ′ in the general formula (II-AB) is, for example, a chlorine atom, a bromine atom, a fluorine atom or an iodine atom.
The alkyl group as R ₁₁ ′ or R ₁₂ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a linear group Or a branched butyl group, a pentyl group, a hexyl group, and a heptyl group are mentioned.
The atomic group represented by Z ′ is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin. As this atomic group, those forming a repeating unit of a bridged alicyclic hydrocarbon are preferable.
Examples of the skeleton of the alicyclic hydrocarbon formed include the same cycloalkyl groups as R _{12 to} R ₂₅ in the general formulas (pI) to (pVI).
The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the above general formulas (II-AB1) and (II-AB2).
In the alicyclic hydrocarbon-based acid-decomposable resin, the group that is decomposed by the action of an acid is a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pI) to the general formula (pV) , And at least one of the repeating unit represented by the general formula (II-AB) and the repeating unit of the copolymerization component to be described later.
Each substituent of R ₁₃ ′ to R ₁₆ ′ in the general formulas (II-AB1) and (II-AB2) is an alicyclic structure or a bridged alicyclic structure in the general formula (II-AB). It can also be a substituent of the atomic group Z ′ to form.
Specific examples of the repeating unit represented by the general formula (II-AB1) or (II-AB2) include the following specific examples, but the present invention is not limited to these examples.

The resin (C) preferably has a repeating unit containing a lactone group. This lactone group is preferably a group having a 5- to 7-membered ring lactone structure, and in particular, other ring structures are condensed to form a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure. Is preferred.
More preferably, the resin (C) includes a repeating unit having a group containing a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures include (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17). . By using specific lactone structures, line edge roughness and development defects can be further reduced.

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferable substituents (Rb ₂ ) include, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, Examples include a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group.
n ₂ represents an integer of 0-4. When n ₂ is an integer of 2 or more, a plurality of Rb ₂ may be the same or different from each other. In this case, a plurality of Rb ₂ may be bonded to each other to form a ring structure.
As the repeating unit having a group containing a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-17), for example, in the above general formulas (II-AB1) and (II-AB2) Wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by general formula (LC1-1) to (LC1-17), and a repeating unit represented by general formula (AI) below Is mentioned. Examples of the former include structures in which R _{5 of} —COOR ₅ is a group represented by general formulas (LC1-1) to (LC1-17).

In General Formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
The alkyl group as Rb ₀ is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a t-butyl group. These alkyl groups may have a substituent. Examples of this substituent include a hydroxyl group and a halogen atom.
Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Rb ₀ is preferably a hydrogen atom or a methyl group.
Ab represents an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, or a combination thereof. Ab is preferably a single bond or a linking group represented by —Ab ₁ —CO ₂ —.
Ab ₁ is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V is a group represented by any one of the general formulas (LC1-1) to (LC1-17).
The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity thereof is preferably 90% ee or more, more preferably 95% ee or more.
Particularly preferred repeating units having a lactone group include the following repeating units. By selecting an optimal lactone group, the pattern profile and the density dependency are improved. In the formula, Rx and R represent H, CH ₃ , CH ₂ OH or CF ₃ .

The resin (C) may contain a plurality of repeating units containing a lactone group. In this case, (1) In formula (AI) Ab is a is one and _-Ab 1 -CO ₂ single bond - used by one those which are, (2) in the general formula (AI) Ab is -Ab ₁ -CO ₂ - a combination of two or what is the preferred one of the.
The repeating unit containing a lactone group is preferably 3 to 70 mol% in the total repeating units of the resin (C) (when there are repeating units containing a plurality of lactone groups, the sum thereof). More preferably, it is -60 mol%.
The resin (C) preferably has a repeating unit containing an alicyclic hydrocarbon structure substituted with a polar group. Thereby, substrate adhesiveness and developer affinity can be improved. As this polar group, a hydroxyl group or a cyano group is preferable. In addition, the hydroxyl group as a polar group forms an alcoholic hydroxyl group.
Examples of the alicyclic hydrocarbon structure substituted with a polar group include structures represented by the following general formula (VIIa) or (VIIb).

In General Formula (VIIa), R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. More preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the remaining one is a hydrogen atom.
The group represented by the general formula (VIIa) is preferably a dihydroxy body or a monohydroxy body, and more preferably a dihydroxy body.
The repeating unit having a group represented by the general formula (VIIa) or (VIIb) includes at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2). Examples thereof include those having a group represented by the general formula (VIIa) or (VIIb) and repeating units represented by the following general formula (AIIa) or (AIIb). Examples of the former include structures in which R _{5 of} —COOR ₅ is a group represented by the general formula (VIIa) or (VIIb).

In general formulas (AIIa) and (AIIb),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c have the same meanings as _R 2 c to R ₄ c in the general formula (VIIa).
Specific examples of the repeating unit represented by the general formula (AIIa) or (AIIb) are shown below, but the present invention is not limited thereto.

The resin (C) may or may not contain the above repeating unit. However, when it is contained, the above repeating unit is (as a sum of those when there are a plurality of corresponding repeating units) of the resin. It is preferable that it is 3-30 mol% in all the repeating units, and it is more preferable that it is 5-25 mol%.
Resin (C) may have a repeating unit represented by the following general formula (VIII).

In General Formula (VIII), Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . Wherein R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group as R ₄₁ or R ₄₂ may be substituted with a halogen atom or the like. In this case, the halogen atom is preferably a fluorine atom.
Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but the present invention is not limited thereto.

The resin (C) preferably has a repeating unit containing an alkali-soluble group, and more preferably has a repeating unit containing a carboxyl group. Thereby, the resolution in contact hole use can be improved.
As the repeating unit containing a carboxyl group, any of a repeating unit in which a carboxyl group is directly bonded to the main chain of the resin and a repeating unit in which a carboxyl group is bonded to the main chain of the resin via a linking group preferable.
As an example of the former, a repeating unit by acrylic acid or methacrylic acid can be mentioned. The linking group in the latter may have a monocyclic or polycyclic cycloalkyl structure.
The repeating unit containing a carboxyl group is most preferably a repeating unit of acrylic acid or methacrylic acid.
The weight average molecular weight of the resin that decomposes by the action of an acid and increases the solubility in an alkaline developer is preferably in the range of 2,000 to 200,000 as a polystyrene conversion value determined by the GPC method. By setting the weight average molecular weight to 2,000 or more, heat resistance and dry etching resistance can be particularly improved. When the weight average molecular weight is 200,000 or less, the developability can be particularly improved, and the film forming property can also be improved due to the decrease in the viscosity of the composition.
A more preferable molecular weight is in the range of 2,500 to 50,000, and still more preferably in the range of 3,000 to 20,000. Moreover, in the fine pattern formation using an electron beam, X-rays, and a high energy ray (for example, EUV) having a wavelength of 50 nm or less, the weight average molecular weight is most preferably in the range of 3,000 to 10,000. By adjusting the molecular weight, an improvement in the heat resistance and resolution of the composition and a reduction in development defects can be achieved at the same time.
The resin dispersibility (Mw / Mn) which decomposes by the action of an acid and increases the solubility in an alkali developer is preferably from 1.0 to 3.0, more preferably from 1.2 to 2.5. 2 to 1.6 is more preferable. By adjusting the degree of dispersion, for example, the line edge roughness performance can be improved.

  Although the specific example of resin demonstrated above is shown below, this invention is not limited to these.

In the above specific example, tBu represents a t-butyl group.
Resin (C) may be used individually by 1 type, and may be used in combination of 2 or more type.
The blending ratio of the resin (C) in the composition according to the present invention is preferably 5 to 99.9% by mass, more preferably 50 to 95% by mass, based on the total solid content, and 60 to 93% by mass. Is more preferable.

[4] (E) Compound having phenolic hydroxyl group When the chemically amplified resist composition of the present invention forms a negative pattern, the compound (E) having a phenolic hydroxyl group (hereinafter also referred to as compound (E)). ) Is preferably contained.
The phenolic hydroxyl group in the present application is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxy group. The aromatic ring of the aromatic ring group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.
According to the chemically amplified resist composition of the present invention, in the exposed portion, an acid generated from the compound (B) that generates an acid upon irradiation with actinic rays or radiation, and the above-mentioned general formula (I) by the action of the acid By the action of the sulfonic acid generated from the represented compound (A), a crosslinking reaction of the compound (E) having a phenolic hydroxyl group and a crosslinking agent (D) described later proceeds, and a negative pattern is formed.

The compound (E) having a phenolic hydroxyl group is not particularly limited as long as it has a phenolic hydroxyl group, and may be a relatively low molecular weight compound such as a molecular resist or a polymer compound. As the molecular resist, for example, low molecular weight cyclic polyphenol compounds described in JP 2009-173623 A and JP 2009-173625 A can be used.
The compound (E) having a phenolic hydroxyl group is preferably a polymer compound from the viewpoints of reactivity and sensitivity.

  When the compound (E) having a phenolic hydroxyl group of the present invention is a polymer compound, the polymer compound preferably contains a repeating unit having at least one phenolic hydroxyl group. Although it does not specifically limit as a repeating unit which has a phenolic hydroxyl group, It is preferable that it is a repeating unit represented by following General formula (1).

In general formula (1), R ₁₁ represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom.
B ₁ represents a single bond or a divalent linking group.
Ar represents an aromatic ring.
m1 represents an integer of 1 or more.

Examples of the methyl group optionally having a substituent for R ₁₁ include a trifluoromethyl group and a hydroxymethyl group.
R ₁₁ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom for reasons of developability.

Examples of the divalent linking group for B ₁ include a carbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group (—S (═O) ₂ —), —O. -, -NH- or a divalent linking group in combination of these is preferred.
B ₁ preferably represents a single bond, a carbonyloxy group (—C (═O) —O—) or —C (═O) —NH—, and a single bond or a carbonyloxy group (—C (═O)) -O-) is more preferable, and a single bond is particularly preferable from the viewpoint of improving dry etching resistance.

The aromatic ring of Ar is a monocyclic or polycyclic aromatic ring, and may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring. Aromatic hydrocarbon ring or, for example, thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc. Aromatic heterocycles including heterocycles can be mentioned. Among these, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable from the viewpoint of sensitivity.
m1 is preferably an integer of 1 to 5, and most preferably 1. When m1 is 1 and Ar is a benzene ring, —OH is substituted at the para position or the meta position relative to the bonding position of the benzene ring with B ₁ (or the polymer main chain when B ₁ is a single bond). However, although it may be ortho-position, from the viewpoint of crosslinking reactivity, para-position and meta-position are preferable, and para-position is more preferable.

  The aromatic ring of Ar may have a substituent other than the group represented by -OH, and examples of the substituent include an alkyl group, a cycloalkyl group, a halogen atom, a hydroxyl group, an alkoxy group, and a carboxyl group. Group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylsulfonyloxy group, and arylcarbonyl group.

  The repeating unit having a phenolic hydroxyl group is more preferably a repeating unit represented by the following general formula (2) for reasons of cross-linking reactivity, developability, and dry etching resistance.

In General Formula (2), R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring.

R ₁₂ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom for reasons of developability.
Ar in General formula (2) is synonymous with Ar in General formula (1), and its preferable range is also the same. The repeating unit represented by the general formula (2) is a repeating unit derived from hydroxystyrene (that is, a repeating unit in which R ₁₂ is a hydrogen atom and Ar is a benzene ring in the general formula (2)). Is preferable from the viewpoint of sensitivity.

  The compound (E) as the polymer compound may be composed only of a repeating unit having a phenolic hydroxyl group as described above. The compound (E) as the polymer compound may have a repeating unit as described later in addition to the repeating unit having a phenolic hydroxyl group as described above. In that case, it is preferable that content of the repeating unit which has a phenolic hydroxyl group is 10-98 mol% with respect to all the repeating units of the compound (E) as a high molecular compound, and is 30-97 mol%. It is more preferable, and it is still more preferable that it is 40-95 mol%. Thereby, particularly when the resist film is a thin film (for example, when the thickness of the resist film is 10 to 150 nm), the alkali development of the exposed portion in the resist film of the present invention formed using the compound (E) is performed. The dissolution rate with respect to the liquid can be more reliably reduced (that is, the dissolution rate of the resist film using the compound (E) can be controlled to an optimum one more reliably). As a result, the sensitivity can be improved more reliably.

  Hereinafter, although the example of the repeating unit which has a phenolic hydroxyl group is described, it is not limited to this.

Compound (E) is a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure and having a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted, so that a high glass transition temperature (Tg) can be obtained. The dry etching resistance is preferable.
When the compound (E) has the specific structure described above, the glass transition temperature (Tg) of the compound (E) is increased, and a very hard resist film can be formed. Resistance can be controlled. Therefore, the diffusibility of the acid in the exposed portion of actinic rays or radiation such as an electron beam or extreme ultraviolet rays is greatly suppressed, so that the resolution, pattern shape and LER in a fine pattern are further improved. Further, it is considered that the compound (E) having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure contributes to further improvement in dry etching resistance. Furthermore, although details are unknown, the polycyclic alicyclic hydrocarbon structure has a high hydrogen radical donating property and is a photoacid generator (B) Hydrogen source at the time of decomposition of a compound that generates an acid upon irradiation with actinic rays or radiation Therefore, it is presumed that the decomposition efficiency of the photoacid generator is further improved and the acid generation efficiency is further increased, and this is considered to contribute to a better sensitivity.
The above-mentioned specific structure that the compound (E) according to the present invention may have is an aromatic ring such as a benzene ring and a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure. Are linked via an oxygen atom derived from a functional hydroxyl group. As described above, the structure not only contributes to high dry etching resistance, but also can increase the glass transition temperature (Tg) of the compound (E), and a higher resolution is provided by the effect of these combinations. It is estimated to be.

In the present invention, non-acid-decomposable means a property in which a decomposition reaction does not occur due to an acid generated from the compound (B) that generates an acid upon irradiation with actinic rays or radiation.
More specifically, the group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure is preferably a group stable to acids and alkalis. The group stable to acid and alkali means a group that does not exhibit acid decomposability and alkali decomposability. Here, the acid decomposability means a property of causing a decomposition reaction by the action of an acid generated by the compound (B) that generates an acid upon irradiation with actinic rays or radiation. Examples include acid-decomposable groups described in “Repeating unit having acid-decomposable group”.
Alkali decomposability means the property of causing a decomposition reaction by the action of an alkali developer, and the group exhibiting alkali decomposability is contained in a resin suitably used in a positive chemically amplified resist composition. And a group (for example, a group having a lactone structure) that decomposes under the action of a conventionally known alkali developer and increases the dissolution rate in the alkali developer.

The group having a polycyclic alicyclic hydrocarbon structure is not particularly limited as long as it is a monovalent group having a polycyclic alicyclic hydrocarbon structure, but the total number of carbon atoms is preferably 5 to 40, and 7 to 30. It is more preferable that The polycyclic alicyclic hydrocarbon structure may have an unsaturated bond in the ring.
The polycyclic alicyclic hydrocarbon structure in the group having a polycyclic alicyclic hydrocarbon structure means a structure having a plurality of monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon structure. It may be a bridge type. As the monocyclic alicyclic hydrocarbon group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. A structure having a plurality of cyclic alicyclic hydrocarbon groups has a plurality of these groups. The structure having a plurality of monocyclic alicyclic hydrocarbon groups preferably has 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferably has two.
Examples of the polycyclic alicyclic hydrocarbon structure include bicyclo, tricyclo, and tetracyclo structures having 5 or more carbon atoms, and polycyclic cyclostructures having 6 to 30 carbon atoms are preferable. For example, an adamantane structure and a decalin structure , Norbornane structure, norbornene structure, cedrol structure, isobornane structure, bornane structure, dicyclopentane structure, α-pinene structure, tricyclodecane structure, tetracyclododecane structure, and androstane structure. A part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

Preferred examples of the polycyclic alicyclic hydrocarbon structure include an adamantane structure, a decalin structure, a norbornane structure, a norbornene structure, a cedrol structure, a structure having a plurality of cyclohexyl groups, a structure having a plurality of cycloheptyl groups, and a plurality of cyclooctyl groups. And a structure having a plurality of cyclodecanyl groups, a structure having a plurality of cyclododecanyl groups, and a tricyclodecane structure, and an adamantane structure is most preferable from the viewpoint of dry etching resistance (that is, the non-acid-decomposable polycyclic fatty acid). Most preferably, the group having a ring hydrocarbon structure is a group having a non-acid-decomposable adamantane structure).
These polycyclic alicyclic hydrocarbon structures (for structures having a plurality of monocyclic alicyclic hydrocarbon groups, the monocyclic alicyclic hydrocarbon structure corresponding to the monocyclic alicyclic hydrocarbon group (specifically Specifically, chemical formulas of the following formulas (47) to (50))) are shown below.

  Furthermore, the polycyclic alicyclic hydrocarbon structure may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), Aryl group (preferably having 6 to 15 carbon atoms), halogen atom, hydroxyl group, alkoxy group (preferably having 1 to 6 carbon atoms), carboxyl group, carbonyl group, thiocarbonyl group, alkoxycarbonyl group (preferably having 2 to 7 carbon atoms) And a group formed by combining these groups (preferably having a total carbon number of 1 to 30, more preferably a total carbon number of 1 to 15).

Examples of the polycyclic alicyclic hydrocarbon structure include a structure represented by any one of the above formulas (7), (23), (40), (41) and (51), and an arbitrary structure in the structure of the above formula (48). A structure having two monovalent groups each having one hydrogen atom as a bond is preferable, a structure represented by any one of the above formulas (23), (40) and (51), A structure having two monovalent groups each having an arbitrary hydrogen atom in the structure as a bond is more preferable, and a structure represented by the above formula (40) is most preferable.
The group having a polycyclic alicyclic hydrocarbon structure is preferably a monovalent group having any one hydrogen atom in the polycyclic alicyclic hydrocarbon structure as a bond.

  The above-described group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure in which a hydrogen atom of a phenolic hydroxyl group is substituted is a group having the aforementioned non-acid-decomposable polycyclic alicyclic hydrocarbon structure. The compound (E) as a polymer compound is preferably contained as a repeating unit having a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted, and the compound (E) as a repeating unit represented by the following general formula (3) More preferably, it is contained in

In General Formula (3), R ₁₃ represents a hydrogen atom or a methyl group.
X represents a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure.
Ar ₁ represents an aromatic ring.
m2 is an integer of 1 or more.

R ₁₃ in the general formula (3) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.
As the aromatic ring of Ar _{1 in} the general formula (3), for example, an aromatic group optionally having a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, or the like. Hydrocarbon ring or heterocycle such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring Aromatic heterocycles containing can be mentioned. Among these, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable.
The aromatic ring of Ar ₁ may have a substituent other than the group represented by the above -OX, and examples of the substituent include an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group. (Preferably 3 to 10 carbon atoms), aryl group (preferably 6 to 15 carbon atoms), halogen atom, hydroxyl group, alkoxy group (preferably 1 to 6 carbon atoms), carboxyl group, alkoxycarbonyl group (preferably carbon number) 2-7) are mentioned, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable, and an alkoxy group is more preferable.

X represents a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure. Specific examples and preferred ranges of the group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure represented by X are the same as those described above. X is more preferably a group represented by —Y—X ₂ in the general formula (4) described later.
m2 is preferably an integer of 1 to 5, and most preferably 1. When m2 is 1 and Ar ₁ is a benzene ring, the substitution position of —OX may be in the para position, the meta position, or the ortho position with respect to the bonding position of the benzene ring with the polymer main chain. The para position is preferred.

In the present invention, the repeating unit represented by the general formula (3) is preferably a repeating unit represented by the following general formula (4).
When the polymer compound (E) having a repeating unit represented by the general formula (4) is used, the polymer compound (E) has a high Tg and forms a very hard resist film. The dry etching resistance can be controlled more reliably.

In the general formula (4), R ₁₃ represents a hydrogen atom or a methyl group.
Y represents a single bond or a divalent linking group.
X ₂ represents a non-acid-decomposable polycyclic alicyclic hydrocarbon group.

Preferred examples of the repeating unit represented by the general formula (4) used in the present invention are described below.
R ₁₃ in the general formula (4) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.
In general formula (4), Y is preferably a divalent linking group. Preferred groups as the divalent linking group for Y are a carbonyl group, a thiocarbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group, —COCH ₂ —, —NH—. Or a divalent linking group (preferably having a total carbon number of 1 to 20, more preferably a total carbon number of 1 to 10), or more preferably a carbonyl group, —COCH ₂ —, a sulfonyl group, —CONH— , —CSNH—, more preferably a carbonyl group, —COCH ₂ —, and particularly preferably a carbonyl group.

X ₂ represents a polycyclic alicyclic hydrocarbon group and is non-acid-decomposable. The total number of carbon atoms of the polycyclic alicyclic hydrocarbon group is preferably 5 to 40, and more preferably 7 to 30. The polycyclic alicyclic hydrocarbon group may have an unsaturated bond in the ring.
Such a polycyclic alicyclic hydrocarbon group is a group having a plurality of monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon group, and may be a bridged type. The monocyclic alicyclic hydrocarbon group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Having a plurality of groups. The group having a plurality of monocyclic alicyclic hydrocarbon groups preferably has 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferably has two.
Examples of the polycyclic alicyclic hydrocarbon group include a group having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms, and a group having a polycyclic cyclo structure having 6 to 30 carbon atoms is preferable. And adamantyl group, norbornyl group, norbornenyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclododecyl group, and androstanyl group. A part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

The polycyclic alicyclic hydrocarbon groups described above X _2, preferably an adamantyl group, a decalin group, a norbornyl group, a norbornenyl group, a cedrol group, a group having a plurality of cyclohexyl groups, having plural groups cycloheptyl group, a cyclooctyl group A group having a plurality, a group having a plurality of cyclodecanyl groups, a group having a plurality of cyclododecanyl groups, and a tricyclodecanyl group, and an adamantyl group is most preferable from the viewpoint of dry etching resistance. The chemical formula of the polycyclic alicyclic hydrocarbon structure in the polycyclic alicyclic hydrocarbon group of X ₂ is the same as the chemical formula of the polycyclic alicyclic hydrocarbon structure in the group having the polycyclic alicyclic hydrocarbon structure described above. The preferable range is also the same. Examples of the polycyclic alicyclic hydrocarbon group represented by X ₂ include a monovalent group having any one hydrogen atom in the above-described polycyclic alicyclic hydrocarbon structure as a bond.
Further, the alicyclic hydrocarbon group may have a substituent, and examples of the substituent include the same as those described above as the substituent that the polycyclic alicyclic hydrocarbon structure may have.
The substitution position of —O—Y—X ₂ in the general formula (4) may be in the para position, the meta position, or the ortho position with respect to the bonding position of the benzene ring with the polymer main chain, but the para position is preferred.

  In the present invention, the repeating unit represented by the general formula (3) is most preferably a repeating unit represented by the following general formula (4 ').

In General Formula (4 ′), R ₁₃ represents a hydrogen atom or a methyl group.

R ₁₃ in the general formula (4 ′) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.
The substitution position of the adamantyl ester group in the general formula (4 ′) may be in the para position, the meta position, or the ortho position with respect to the bonding position with the polymer main chain of the benzene ring, but the para position is preferred.

  Specific examples of the repeating unit represented by the general formula (3) include the following.

  When the compound (E) is a polymer compound and further contains a repeating unit having a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a group having the non-acid-decomposable polycyclic alicyclic hydrocarbon structure described above. The content of the repeating unit is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, based on all repeating units of the compound (E) as the polymer compound.

  The compound (E) as the polymer compound used in the present invention preferably further has the following repeating units (hereinafter also referred to as “other repeating units”) as repeating units other than the repeating units.

Examples of polymerizable monomers for forming these other repeating units include styrene, alkyl-substituted styrene, alkoxy-substituted styrene, halogen-substituted styrene, O-alkylated styrene, O-acylated styrene, hydrogenated hydroxystyrene, and anhydrous maleic acid. Acid, acrylic acid derivative (acrylic acid, acrylic ester, etc.), methacrylic acid derivative (methacrylic acid, methacrylic ester, etc.), N-substituted maleimide, acrylonitrile, methacrylonitrile, vinyl naphthalene, vinyl anthracene Inden etc. which may be sufficient can be mentioned.
The compound (E) as the polymer compound may or may not contain these other repeating units, but when it is contained, the content of these other repeating units in the compound (E) as the polymer compound Is generally 1 to 30 mol%, preferably 1 to 20 mol%, more preferably 2 to 10 mol%, based on all repeating units constituting the compound (E) as the polymer compound.

The compound (E) as the polymer compound can be synthesized by a known radical polymerization method, anion polymerization method or living radical polymerization method (such as an iniferter method). For example, in an anionic polymerization method, a vinyl monomer can be dissolved in a suitable organic solvent, and a polymer can be obtained by usually reacting under a cooling condition using a metal compound (such as butyl lithium) as an initiator.
As the compound (E) as the polymer compound, an aromatic ketone or aromatic aldehyde, and a polyphenol compound produced by a condensation reaction of a compound containing 1 to 3 phenolic hydroxyl groups (for example, JP 2008-145539 A). ), Calixarene derivatives (for example, Japanese Patent Application Laid-Open No. 2004-18421), Noria derivatives (for example, Japanese Patent Application Laid-Open No. 2009-222920), and polyphenol derivatives (for example, Japanese Patent Application Laid-Open No. 2008-94782) can also be applied. good.
The compound (E) as a polymer compound is preferably synthesized by modifying a polymer synthesized by a radical polymerization method or an anion polymerization method by a polymer reaction.
The weight average molecular weight of the compound (E) as the polymer compound is preferably 1000 to 200000, more preferably 2000 to 50000, and still more preferably 2000 to 15000.
The dispersity (molecular weight distribution) (Mw / Mn) of the compound (E) as the polymer compound is preferably 2.5 or less, and more preferably 1.0 to 2 in terms of improving sensitivity and resolution. 0.5, more preferably 1.0 to 1.6, and most preferably 1.0 to 1.25. Use of living polymerization such as living anionic polymerization is preferable because the degree of dispersion (molecular weight distribution) of the resulting polymer compound becomes uniform. The weight average molecular weight and dispersity of the compound (E) as the polymer compound are defined as polystyrene converted values by GPC measurement.
A compound (E) may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of compound (E) added to the chemically amplified resist composition of the present invention is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass relative to the total solid content of the composition. Used at 85% by weight.

  Specific examples of the compound (E) are shown below, but the present invention is not limited thereto.

[5] (D) Crosslinking agent The chemically amplified resist composition of the present invention contains a crosslinking agent (D) (hereinafter appropriately referred to as an acid crosslinking agent or simply a crosslinking agent) when forming a negative pattern. It is preferable to do.
The chemically amplified resist composition of the present invention more preferably contains a compound having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule as the crosslinking agent (D).

Preferred crosslinking agents include hydroxymethylated or alkoxymethylated phenolic compounds, alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds and alkoxymethylated urea compounds, among which hydroxymethylated or alkoxymethylated compounds. A phenolic phenol compound is more preferable because a good pattern shape can be obtained. As a particularly preferred compound (D) as a crosslinking agent, a phenol derivative containing 3 to 5 benzene rings in the molecule, further having two or more hydroxymethyl groups or alkoxymethyl groups, and having a molecular weight of 1200 or less. And melamine-formaldehyde derivatives and alkoxymethylglycoluril derivatives having at least two free N-alkoxymethyl groups.
The chemically amplified resist composition of the present invention preferably contains at least two compounds having two or more alkoxymethyl groups in the molecule as the crosslinking agent (D) from the viewpoint of pattern shape. It is further preferable to contain at least two phenol compounds having 2 or more in the molecule, and at least one of the at least two phenol compounds contains 3 to 5 benzene rings in the molecule, and further alkoxy. Particularly preferred is a phenol derivative having two or more methyl groups and a molecular weight of 1200 or less.
As the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable.

Among the crosslinking agents, a phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound not having a hydroxymethyl group with formaldehyde under a base catalyst. A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst.
Of the phenol derivatives synthesized as described above, a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of sensitivity and storage stability.

  Examples of another preferable crosslinking agent further include compounds having an N-hydroxymethyl group or an N-alkoxymethyl group, such as alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds, and alkoxymethylated urea compounds. be able to.

Examples of such compounds include hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl glycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethylene urea, bismethoxymethyl urea, and the like. 133, 216A, West German Patent No. 3,634,671, No. 3,711,264, EP 0,212,482A.
Particularly preferred among these crosslinking agents are listed below.

In the formula, L _{1 to} L ₈ each independently represent a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.

  In the present invention, the crosslinking agent is preferably used in an amount of 3 to 65% by mass, more preferably 5 to 50% by mass, and more preferably 5 to 30% by mass in the solid content of the resist composition. By making the addition amount of the crosslinking agent 3 to 65% by mass, it is possible to prevent the remaining film ratio and the resolution from being lowered, and to maintain good stability during storage of the resist solution.

In this invention, a crosslinking agent may be used independently, may be used in combination of 2 or more types, and it is preferable to use in combination of 2 or more types from a viewpoint of pattern shape.
For example, in addition to the above-mentioned phenol derivative, when another crosslinking agent, for example, the above-mentioned compound having an N-alkoxymethyl group is used in combination, the ratio of the above-mentioned phenol derivative to the other crosslinking agent is 100/0 in molar ratio. -20/80, preferably 90 / 10-40 / 60, more preferably 80 / 20-50 / 50.

[6] Basic Compound The chemically amplified resist composition of the present invention preferably contains a basic compound as an acid scavenger in addition to the above components. By using a basic compound, a change in performance over time from exposure to post-heating can be reduced. Such basic compounds are preferably organic basic compounds, and more specifically, aliphatic amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, and sulfonyl groups. A nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like. An amine oxide compound (a compound having a methyleneoxy unit and / or an ethyleneoxy unit is preferable, for example, a compound described in JP-A-2008-102383), an ammonium salt (preferably a hydroxide or a carboxylate). In particular, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable from the viewpoint of LER.
Furthermore, a compound whose basicity is increased by the action of an acid can also be used as one kind of basic compound.
Specific examples of amines include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, tetradecylamine, pentadecylamine. , Hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N-dihexylaniline, 2,6- Diisopropylaniline, 2,4,6-tri (t-butyl) aniline, triethanolamine, N, N-dihydroxyethylaniline, tris (methoxyethoxyethyl) amine, and columns 3, 60 of US Pat. No. 6,040,112. Beyond And 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and U.S. Patent Application Publication No. 2007 / 0224539A1. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above. Examples of the compound having a nitrogen-containing heterocyclic structure include 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, N-hydroxyethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl ) Sebacate, 4-dimethylaminopyridine, antipyrine, hydroxyantipyrine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] -undec-7-ene And tetrabutylammonium hydroxide.
Photodegradable basic compounds (initially basic nitrogen atoms act as a base and show basicity, but are decomposed by irradiation with actinic rays or radiation to have amphoteric compounds having basic nitrogen atoms and organic acid sites. Compounds in which basicity is reduced or eliminated by generating ionic compounds and neutralizing them in the molecule, for example, Toho 3577743, JP 2001-215589 A, JP 2001-166476 A, JP 2008-102383 A Onium salts) and photobase generators (for example, compounds described in JP2010-243773) are also used as appropriate.
Among these basic compounds, an ammonium salt or a photodegradable basic compound is preferable because good LER can be obtained.
In this invention, a basic compound may be used independently and may be used in combination of 2 or more type.
The content of the basic compound used in the present invention is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and more preferably 0.05 to 5% by mass with respect to the total solid content of the resist composition. 3% by mass is particularly preferred.

[7] Surfactant The chemically amplified resist composition of the present invention may further contain a surfactant in order to improve coatability. Examples of surfactants include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Nonionic surfactants such as sorbitan fatty acid esters, Megafac F171 and F176 (manufactured by Dainippon Ink and Chemicals), Florard FC430 (manufactured by Sumitomo 3M), Surfinol E1004 (manufactured by Asahi Glass), PF656 and PF6320 manufactured by OMNOVA, etc. And an organosiloxane polymer such as polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
When the resist composition contains a surfactant, the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0005, based on the total amount of the resist composition (excluding the solvent). ˜1% by mass.

[8] Organic Carboxylic Acid The chemically amplified resist composition of the present invention preferably contains an organic carboxylic acid in addition to the above components from the viewpoint of scum characteristics. Examples of such organic carboxylic acid compounds include aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated aliphatic carboxylic acids, oxycarboxylic acids, alkoxycarboxylic acids, ketocarboxylic acids, benzoic acids, benzoic acid derivatives, phthalic acid, terephthalic acid , Isophthalic acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, and the like. As a preferable compound, aromatic organic carboxylic acid, among them, benzoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, among others, may be contaminated. Is preferred.
As a compounding quantity of organic carboxylic acid, the inside of the range of 0.01-10 mass parts is preferable with respect to 100 mass parts of compounds (E) which have a phenolic hydroxyl group, More preferably, it is 0.01-5 mass parts, and still more. Preferably it is 0.01-3 mass parts.

If necessary, the chemically amplified resist composition of the present invention may further comprise a dye, a plasticizer, an acid proliferating agent other than the compound (A) (International Publication No. 95/29968, International Publication No. 98/24000). JP-A-8-305262, JP-A-9-34106, JP-A-8-248561, JP-A-8-503082, JP-A-5,445,917, JP-A-8. No. -503081, US Pat. No. 5,534,393, US Pat. No. 5,395,736, US Pat. No. 5,741,630, US Pat. No. 5,334,489 Specification, US Pat. No. 5,582,956, US Pat. No. 5,578,424, US Pat. No. 5,453,345, US Pat. No. 5,445,917 , European Patent No. 65,960, European Patent 757,628, European Patent 665,961, US Pat. No. 5,667,943, Japanese Patent Application Laid-Open No. 10-1508, Japanese Patent Application Laid-Open No. 10 No. -282642, JP-A-9-512498, JP-A-2000-62337, JP-A-2005-17730, JP-A-2008-209889, and the like. As for these compounds, the respective compounds described in JP-A-2008-268935 can be mentioned.
[Carboxylic acid onium salt]
The chemically amplified resist composition of the present invention may contain a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. In particular, the carboxylic acid onium salt is preferably a carboxylic acid iodonium salt or a carboxylic acid sulfonium salt. Furthermore, in this invention, it is preferable that the carboxylate residue of carboxylic acid onium salt does not contain an aromatic group and a carbon-carbon double bond. As a particularly preferred anion moiety, a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferred. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.

Examples of the solvent used in the chemically amplified resist composition of the present invention include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), propylene Glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, β-methoxyiso Methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate Diacetone alcohol, N- methylpyrrolidone, N, N- dimethylformamide, .gamma.-butyrolactone, N, N- dimethylacetamide, propylene carbonate, and ethylene carbonate is preferred. These solvents are used alone or in combination.
It is preferable that the solid content of the resist composition is dissolved in the solvent, and is dissolved at a solid content concentration of 1 to 40% by mass. More preferably, it is 1-30 mass%, More preferably, it is 3-20 mass%.

  The present invention also relates to a resist film formed by the chemically amplified resist composition of the present invention. Such a resist film is formed, for example, by applying the resist composition onto a support such as a substrate. Is done. The thickness of the resist film is preferably 0.02 to 0.1 μm. As a method for coating on the substrate, spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. are applied on the substrate, but spin coating is preferred, and the number of rotations is 1000 to 3000 rpm is preferable. The coating film is pre-baked at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to 120 ° C. for 1 to 10 minutes to form a thin film.

For example, in the case of a semiconductor wafer, a silicon wafer can be used as the material constituting the substrate to be processed and its outermost layer. Examples of the material that becomes the outermost layer include Si, SiO ₂ , SiN, SiON, TiN, and WSi. , BPSG, SOG, organic antireflection film, and the like.

The present invention also relates to a resist coating mask blank coated with the resist film obtained as described above. In order to obtain such a resist-coated mask blank, when forming a resist pattern on a photomask blank for producing a photomask, examples of the transparent substrate used include transparent substrates such as quartz and calcium fluoride. it can. In general, a light-shielding film, an antireflection film, a phase shift film, and additional functional films such as an etching stopper film and an etching mask film are laminated on the substrate. As a material for the functional film, a film containing a transition metal such as silicon or chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium is laminated. In addition, as a material used for the outermost layer, silicon or a material containing oxygen and / or nitrogen in silicon as a main constituent material, and further a silicon compound material containing a transition metal-containing material as a main constituent material Or a transition metal, in particular, one or more selected from chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium, etc., or a material further containing one or more elements selected from oxygen, nitrogen, and carbon The transition metal compound material is exemplified.
The light shielding film may be a single layer, but more preferably has a multilayer structure in which a plurality of materials are applied. In the case of a multilayer structure, the thickness of the film per layer is not particularly limited, but is preferably 5 nm to 100 nm, and more preferably 10 nm to 80 nm. Although it does not specifically limit as thickness of the whole light shielding film, It is preferable that it is 5 nm-200 nm, and it is more preferable that it is 10 nm-150 nm.

Of these materials, when pattern formation is performed using a negative chemically amplified resist composition on a photomask blank that generally contains a material containing oxygen or nitrogen in chromium as the outermost layer, the constriction shape is near the substrate. Although the so-called undercut shape is likely to be formed, the use of the present invention can improve the undercut problem as compared with the conventional one.
Next, the resist film is irradiated with actinic rays or radiation (such as an electron beam), and preferably baked (usually 80 to 150 ° C., more preferably 90 to 130 ° C., usually 1 to 20 minutes, preferably 1 to 10). ) And then develop. Thereby, a good pattern can be obtained. Then, using this pattern as a mask, etching processing, ion implantation, and the like are performed as appropriate to create a semiconductor microcircuit, an imprint mold structure, a photomask, and the like.
In addition, about the process in the case of producing the mold for imprinting using the composition of this invention, patent 4109085 gazette, Unexamined-Japanese-Patent No. 2008-162101, and "the foundation of nanoimprint, technical development, and application development, for example" -Nanoimprint substrate technology and latest technology development-edited by Yoshihiko Hirai (Frontier Publishing) ".

The usage pattern of the chemically amplified resist composition of the present invention and the resist pattern forming method will be described below.
The present invention also relates to a resist pattern forming method including exposing the resist film or the resist-coated mask blank and developing the exposed resist film or the resist-coated mask blank. In the present invention, the exposure is preferably performed using an electron beam or extreme ultraviolet rays.
In the production of a precision integrated circuit element or the like, the exposure (pattern formation step) on the resist film is preferably performed by first irradiating the resist film of the present invention with an electron beam or extreme ultraviolet rays (EUV). In the case of an electron beam, the exposure amount is about 0.1 to 20 μC / cm ² , preferably about 3 to 15 μC / cm ² , and in the case of extreme ultraviolet light, about 0.1 to 20 mJ / cm ² , preferably about 3 to 15 mJ / cm ^2. It exposes so that it may become. Next, post-exposure heating (post-exposure baking) is performed on a hot plate at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to 120 ° C. for 1 to 10 minutes, followed by development, rinsing and drying. Form a pattern. The developer is preferably 0.1 to 5% by mass, more preferably 2-3% by mass alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TBAH), preferably 0.1%. Development is performed by a conventional method such as a dip method, a paddle method, or a spray method for ˜3 minutes, more preferably 0.5 to 2 minutes. An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer. The pH of the alkali developer is usually from 10.0 to 15.0. In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.

An appropriate amount of alcohol and / or surfactant can be added to the developer as necessary.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-334540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

  Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

  Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using a developing solution.

  As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.

  Thus, when the chemically amplified resist composition of the present invention is a negative type, the resist film in the unexposed portion is dissolved, and the exposed portion is hardly dissolved in the developer because the polymer compound is cross-linked. When the chemically amplified resist composition is a positive type, the exposed portion is dissolved in the developer, and the unexposed portion is hardly dissolved in the developer, and a target pattern is formed on the substrate.

The present invention also relates to a photomask obtained by exposing and developing a resist-coated mask blank. The steps described above are applied as exposure and development. The photomask is suitably used for semiconductor manufacturing.
The photomask in the present invention may be a light transmissive mask used in an ArF excimer laser or the like, or a light reflective mask used in reflective lithography using EUV light as a light source.

The present invention also relates to a semiconductor device manufacturing method including the above-described resist pattern forming method of the present invention, and a semiconductor device manufactured by this manufacturing method.
The semiconductor device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.
Hereinafter, Examples 7P, 10P, and 3Q are each replaced with reference examples.

[Synthesis of Compound (A)]
<Synthesis Example 1: Synthesis of Compound (A1)>
10 g of 3-methyl-1,3-butanediol was dissolved in 200 mL of acetonitrile, 14.6 g of triethylamine and 235 mg of 4-dimethylaminopyridine were added, and then 2,4,6-triisopropylbenzenesulfonic acid chloride 29. 1 g was added and stirred at room temperature for 4 hours. Ethyl acetate 100mL and distilled water 100mL were added to the reaction liquid, it moved to the separating funnel, and the aqueous layer was removed. Thereafter, the organic layer was washed three times with 200 mL of distilled water, and then the organic layer was concentrated. The concentrate is purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane (mass ratio) = 10/1), and the solvent is distilled off under reduced pressure, followed by vacuum drying to obtain 30.7 g of compound (A0). It was.
¹ H-NMR (CDCl ₃ : ppm) δ: 1.33 to 1.22 (18H, m), 1.92 (2H, t, J = 7.1 Hz), 2.97 to 2.85 (1H, m), 4.20-4.10 (2H, m), 4.23 (2H, t, J = 7.2 Hz), 7.18 (2H, s)

1.0 g of compound (A0) was dissolved in 5 mL of acetonitrile, and 413 mg of acetic anhydride and 7.4 mg of cerium trifluoromethanesulfonate were added and stirred at room temperature for 24 hours. Ethyl acetate 50mL and distilled water 50mL were added to the reaction liquid, it moved to the separating funnel, and the aqueous layer was removed. Thereafter, the organic layer was washed 3 times with 50 mL of distilled water, and then the organic layer was concentrated. The concentrate was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 5/1), and the solvent was distilled off under reduced pressure, followed by vacuum drying to obtain 670 mg of compound (A1).
¹ H-NMR (CDCl ₃ : ppm) δ: 1.54 to 1.25 (18H, m), 1.46 (6H, s), 1.90 (3H, m), 2.17 (2H, t , J = 7.0 Hz), 2.93 to 2.90 (1H, m), 4.17 to 4.09 (4H, m), 7.19 (2H, s)

Similarly, compounds (A2) to (A14) were also synthesized by reacting an alcohol compound with an acid anhydride or acid chloride in the presence of an acid catalyst.
Comparative compounds (AC1) to (AC4) were prepared as compounds not corresponding to the general formula (I).
Furthermore, the value which calculated the volume of the sulfonic acid which these compounds generate | occur | produce by the above-mentioned method using "WinMOPAC" made from Fujitsu Ltd. was shown with following Tables 1-3 with the structure of these compounds. The comparative compound (AC4) is a 1,4-diol derivative and does not function as an acid proliferating agent as described above. However, the volume of the sulfonic acid when it is assumed that sulfonic acid is generated is convenient. It is described in.

[Example 1P] (Electron beam exposure; positive type)
(1) Preparation of Support A 6-inch wafer on which Cr oxide was vapor-deposited (prepared with a shielding film used for ordinary photomask blanks) was prepared.

(2) Preparation of resist coating solution (coating solution composition of positive chemically amplified resist composition P1)
Compound (A1) 0.3 g
9.7 g of polymer compound (P-4)
Photoacid generator z5 (the structural formula is shown below) 0.3 g
Tetrabutylammonium hydroxide (basic compound) 0.02g
Surfactant PF6320 (manufactured by OMNOVA) 0.01 g
Propylene glycol monomethyl ether acetate (solvent) 18.0g

  The composition solution was microfiltered with a polytetrafluoroethylene filter having a pore size of 0.04 μm to obtain a resist coating solution having a solid content concentration of 3.84% by mass.

(3) Preparation of resist film A resist coating solution is applied on the 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron, and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 100 nm. It was. That is, resist-coated mask blanks were obtained.

(4) Production of Positive Resist Pattern Pattern irradiation was performed on this resist film using an electron beam lithography apparatus (manufactured by Elionix Corporation; ELS-7500, acceleration voltage 50 KeV). After irradiation, it was heated on a hot plate at 120 ° C. for 90 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried.

(5) Evaluation of resist pattern The obtained pattern was evaluated for sensitivity, resolving power, pattern shape, line edge roughness (LER) and dry etching resistance by the following methods.

〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount (electron beam irradiation amount) when resolving a resist pattern having a line width of 100 nm (line: space = 1: 1) was defined as sensitivity. The smaller this value, the higher the sensitivity.

[Resolution Evaluation (LS)]
The limit resolving power (minimum line width at which lines and spaces are separated and resolved) at the exposure amount (electron beam irradiation amount) showing the above sensitivity was defined as LS resolving power.

[Resolution Evaluation (IL)]
The critical resolution (minimum line width at which lines and spaces are separated and resolved) at the minimum dose when resolving an isolated line pattern (line: space = 1:> 100) with a line width of 100 nm is defined as IL resolution (nm). did.

[Pattern shape]
Using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), the cross-sectional shape of a line pattern (L / S = 1/1) having a line width of 100 nm at the exposure amount (electron beam irradiation amount) showing the sensitivity described above. And observed. In the cross-sectional shape of the line pattern, the ratio represented by [line width at the bottom part (bottom part) of the line pattern / line width at the middle part of the line pattern (half height position of the line pattern)] is 1.5. Evaluation was made with the above as “forward taper”, the ratio of 1.2 or more and less than 1.5 as “slightly forward taper”, and the ratio of less than 1.2 as “rectangular” .

[Line edge roughness (LER)]
A line pattern (L / S = 1/1) having a line width of 100 nm was formed with an irradiation amount (electron beam irradiation amount) showing the above sensitivity. And about arbitrary 30 points | pieces contained in the length direction 50 micrometers, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. A smaller value indicates better performance.

[Scum evaluation]
A line pattern was formed by the same method as in the above [Pattern shape]. Thereafter, a cross-sectional SEM was obtained by S4800 (manufactured by Hitachi High-Tech Co., Ltd.), and the residue in the space portion was observed and evaluated as follows.
X: Scum is seen and patterns are partially connected.
○: Scum is seen but the patterns are not connected.
A: Scum is not seen.
[Dry etching resistance evaluation]
The unexposed resist film was dry-etched with HITACHI U-621 for 30 seconds using Ar / C ₄ F ₆ / O ₂ gas (mixed gas with a volume ratio of 100/4/2). Thereafter, the resist remaining film ratio was measured and used as an index of dry etching resistance.
Very good: remaining film rate of 95% or more Good: less than 95% 90% or more Poor: less than 90%

[Stability over time]
After each composition was stored at room temperature for 1 month, the degree of change in sensitivity before and after storage (sensitivity measured in the above [sensitivity]) was evaluated. This evaluation was performed based on the following criteria.
(Criteria)
○ (Good): When the variation in sensitivity was less than 1 μC / cm ² Δ (Fair): When the variation in sensitivity was 1 μC / cm ² or more and 3 μC / cm ² or less × (Insufficient): Sensitivity When the fluctuation of was larger than 3 μC / cm ² .

[Example 2P] to [Example 28P], [Comparative Example 1P] to [Comparative Example 5P]
Resist solution formulation with a solid content concentration of 3.84% by mass (positive resist compositions P2 to P28, positive resist comparison composition) in the same manner as in Example 1P except for the components listed in Tables 4 to 6 below. Preparation of P1 to P5), positive pattern formation and evaluation thereof were performed.

  Abbreviations of materials other than the above used in the above-mentioned examples / comparative examples are described below.

[Acid generator (compound (B))]

[Resin (C)]

[Basic compounds]
B1: Tetrabutylammonium hydroxide B2: Tri (n-octyl) amine B3: 2,4,5-triphenylimidazole

[Surfactant]
W-1: PF6320 (manufactured by OMNOVA)
W-2: Megafuck F176 (Dainippon Ink Chemical Co., Ltd .; fluorine-based)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)

〔solvent〕
S1: Propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxypropane)
S2: Propylene glycol monomethyl ether (1-methoxy-2-propanol)
S3: 2-heptanone S4: Ethyl lactate S5: Cyclohexanone S6: γ-butyrolactone S7: Propylene carbonate

  Table 7 shows the evaluation results.

As is apparent from the results shown in Table 7, Comparative Example 1P using no acid proliferating agent and Comparative Examples 2P to 5P using an acid proliferating agent not satisfying the general formula (I) are sensitive, resolving power, pattern shape, LER. It can be seen that the dry etching resistance is poor. Moreover, it turns out that scum reduction is also inferior about Comparative Example 1P, 4P, 5P, and temporal stability is also inferior about Comparative Example 2P-5P.
On the other hand, it can be seen that Examples 1P to 28P using the acid proliferating agent satisfying the general formula (I) are particularly excellent in scum reduction and excellent in sensitivity, resolution, pattern shape, LER, dry etching resistance, and stability over time.

[Example as positive chemically amplified resist (EUV)]
[Examples 1Q to 9Q and Comparative Examples 1Q to 5Q]
(Preparation of resist solution)
The positive resist composition shown in Table 8 below was filtered through a polytetrafluoroethylene filter having a pore size of 0.04 μm to prepare a positive resist solution having a solid content concentration of 3.84% by mass.

(Resist evaluation)
The prepared positive resist solution was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and then heated and dried on a hot plate at 100 ° C. for 60 seconds to obtain 0.05 μm. A resist film having a film thickness was formed.
The obtained resist film was evaluated for sensitivity, resolution, pattern shape, line edge roughness (LER) and dry etching resistance by the following methods.

〔sensitivity〕
Using the EUV light (wavelength 13 nm) to the obtained resist film, the exposure amount was changed by 0.1 mJ / cm ^{2 in} the range of 0 to 20.0 mJ / cm ^2, while the 1: 1 line and After exposure through a space pattern reflective mask, the substrate was baked at 110 ° C. for 90 seconds. Then, it developed using the 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution.
The exposure amount for reproducing a line and space (L / S = 1/1) mask pattern having a line width of 100 nm was defined as sensitivity. The smaller this value, the higher the sensitivity.

[Resolution]
The resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the exposure amount showing the above sensitivity.

[Pattern shape]
The cross-sectional shape of a line pattern (L / S = 1/1) having a line width of 100 nm at the exposure amount showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). In the cross-sectional shape of the line pattern, the ratio represented by [line width at the bottom part (bottom part) of the line pattern / line width at the middle part of the line pattern (half height position of the line pattern)] is 1.5. Evaluation was made with the above as “forward taper”, the ratio of 1.2 or more and less than 1.5 as “slightly forward taper”, and the ratio of less than 1.2 as “rectangular” .

[Line edge roughness (LER)]
A line pattern (L / S = 1/1) having a line width of 100 nm was formed with the exposure amount showing the above sensitivity. And about the arbitrary 30 points | pieces in the length direction 50 micrometers, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. A smaller value indicates better performance.

[Dry etching resistance]
The unexposed resist film was dry-etched with HITACHI U-621 for 15 seconds using Ar / C ₄ F ₆ / O ₂ gas (mixed gas with a volume ratio of 100/4/2). Thereafter, the resist remaining film ratio was measured and used as an index of dry etching resistance.
Very good: remaining film rate of 95% or more Good: less than 95% 90% or more Poor: less than 90%

[Stability over time]
After each composition was stored at room temperature for 1 month, the degree of change in sensitivity before and after storage (sensitivity measured in the above [sensitivity]) was evaluated. This evaluation was performed based on the following criteria.
(Criteria)
○ (Good): when the change in sensitivity is less than ^{1mJ / cm 2 △ (Fair)} : variation in sensitivity 1 mJ / cm ² or more, and, 3 mJ / cm ² or less which was a case × (Insufficient): Sensitivity When the fluctuation was greater than 3 mJ / cm ² .
[Scum evaluation]
A line pattern was formed by the same method as in the above [Pattern shape]. Thereafter, a cross-sectional SEM was obtained by S4800 (manufactured by Hitachi High-Tech Co., Ltd.), and the residue in the space portion was observed and evaluated as follows.
X: Scum is seen and patterns are partially connected.
○: Scum is seen but the patterns are not connected.
A: Scum is not seen.

  The above evaluation results are shown in Table 8.

As is apparent from the results shown in Table 8, Comparative Example 1Q in which no acid proliferating agent is used and Comparative Examples 2Q to 5Q in which an acid proliferating agent not satisfying the general formula (I) is used are sensitivity, resolution, pattern shape, It turns out that it is inferior to LER and dry etching tolerance. Further, it can be seen that Comparative Examples 1Q, 4Q, and 5Q are inferior in scum reduction, and Comparative Examples 2Q to 5Q are also inferior in stability over time.
On the other hand, it can be seen that Examples 1Q to 9Q using the acid proliferating agent satisfying the general formula (I) are particularly excellent in scum reduction and excellent in sensitivity, resolution, pattern shape, LER, dry etching resistance and stability over time.

[Examples 1E to 30E and Comparative Examples 1E to 5E (electron beam exposure; negative type)]
(1) Preparation of Support A 6-inch wafer on which Cr oxide was vapor-deposited (prepared with a shielding film used for ordinary photomask blanks) was prepared.

(2) Preparation of resist coating solution (coating solution composition of negative chemically amplified resist composition N1)
Compound (A1) (structural formula is the above) 0.47 g
Photoacid generator (z61) (structural formula is below) 0.47 g
Compound (P4) (structural formula is shown below) 4.21 g
Cross-linking agent CL-1 (structural formula below) 0.59 g
Cross-linking agent CL-4 (the structural formula is shown below) 0.30 g
Tetrabutylammonium hydroxide (basic compound) 0.04g
2-hydroxy-3-naphthoic acid (organic carboxylic acid) 0.11 g
Surfactant PF6320 (manufactured by OMNOVA) 0.005g
Propylene glycol monomethyl ether acetate (solvent) 18.8g
Propylene glycol monomethyl ether (solvent) 75.0 g

The composition solution was microfiltered with a polytetrafluoroethylene filter having a pore size of 0.04 μm to obtain a resist coating solution.
Negative chemically amplified resist compositions N2 to N30, negative chemically amplified resist compositions N1 and negative chemically amplified resist compositions N1 except that the components listed in Tables 9 to 11 below were used in the resist formulation. Comparative compositions N1-N5 were prepared.

  Abbreviations of materials other than the above used in the above-mentioned examples / comparative examples are described below.

[Compound having a phenolic hydroxyl group (compound (E))]

[Acid generator (compound (B))]
The acid generator (compound (B)) is as described above.

[Crosslinking agent (compound (D))]

[Basic compounds]
The basic compounds (B1 to B6) are as described above.

[Organic carboxylic acid]
D1: 2-hydroxy-3-naphthoic acid D2: 2-naphthoic acid D3: benzoic acid

[Surfactant]
The surfactants (W-1 to W-3) are as described above.
〔solvent〕
The solvents (S1 to S7) are as described above.

(3) Preparation of resist film A resist coating solution is applied on the 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron, and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 100 nm. It was. That is, resist-coated mask blanks were obtained.

(4) Production of Negative Resist Pattern Pattern irradiation was performed on this resist film using an electron beam drawing apparatus (manufactured by Elionix Co., Ltd .; ELS-7500, acceleration voltage 50 KeV). After irradiation, it was heated on a hot plate at 120 ° C. for 90 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried.

(5) Evaluation of resist pattern The obtained pattern was evaluated for sensitivity, resolution, pattern shape, line edge roughness (LER), dry etching resistance, scum and stability over time by the following methods.

〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount (electron beam irradiation amount) when resolving a resist pattern having a line width of 100 nm (line: space = 1: 1) was defined as sensitivity. The smaller this value, the higher the sensitivity.

[Resolution]
The limiting resolution (minimum line width at which lines and spaces (line: space = 1: 1) are separated and resolved) at the exposure amount (electron beam irradiation amount) showing the above sensitivity was defined as the resolution (nm).

[Pattern shape]
Using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), the cross-sectional shape of a line pattern (L / S = 1/1) having a line width of 100 nm at the exposure amount (electron beam irradiation amount) showing the sensitivity described above. And observed. In the cross-sectional shape of the line pattern, a ratio represented by [line width at the top part (surface part) of the line pattern / line width at the middle part of the line pattern (a half height position of the line pattern)] is 1. Evaluation with 5 or more as “reverse taper”, ratio with 1.2 or more and less than 1.5 as “slightly reverse taper”, and ratio with less than 1.2 as “rectangular” It was.

[Line edge roughness (LER)]
A line pattern (L / S = 1/1) having a line width of 100 nm was formed with an irradiation amount (electron beam irradiation amount) showing the above sensitivity. And about arbitrary 30 points | pieces contained in the length direction 50 micrometers, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. A smaller value indicates better performance.

[Dry etching resistance]
A resist film formed by irradiating the entire surface with an irradiation amount (electron beam irradiation amount) exhibiting the above sensitivity was subjected to Ar / C ₄ F ₆ / O ₂ gas (volume ratio of 100/4/2) with HITACHI U-621. Using a mixed gas), dry etching was performed for 30 seconds. Thereafter, the resist remaining film ratio was measured and used as an index of dry etching resistance.
Very good: remaining film rate of 95% or more Good: less than 95% 90% or more Poor: less than 90%

[Scum evaluation]
A line pattern was formed by the same method as in the above [Pattern shape]. Thereafter, a cross-sectional SEM was obtained by S4800 (manufactured by Hitachi High-Tech Co., Ltd.), and the residue in the space portion was observed and evaluated as follows.
X: Scum is seen and patterns are partially connected.
○: Scum is seen but the patterns are not connected.
A: Scum is not seen.

[Stability over time]
After each composition was stored at room temperature for 1 month, the degree of change in sensitivity before and after storage (sensitivity measured in the above [sensitivity]) was evaluated. This evaluation was performed based on the following criteria.
(Criteria)
○ (Good): When the variation in sensitivity was less than 1 μC / cm ² Δ (Fair): When the variation in sensitivity was 1 μC / cm ² or more and 3 μC / cm ² or less × (Insufficient): Sensitivity When the fluctuation of was larger than 3 μC / cm ² .

  The evaluation results are shown in Tables 12 and 13.

As is clear from the results shown in Tables 12 and 13, Comparative Example 1E in which no acid proliferating agent is used and Comparative Examples 2E to 5E in which an acid proliferating agent that does not satisfy the general formula (I) are used are sensitive, resolving power, and pattern. It can be seen that the shape, LER, and dry etching resistance are poor. Moreover, it turns out that scum reduction is also inferior about Comparative Example 1E, 4E, 5E, and temporal stability is also inferior about Comparative Example 2E-5E.
On the other hand, it can be seen that Examples 1E to 30E using the acid proliferating agent satisfying the general formula (I) are particularly excellent in sensitivity and scum reduction, and excellent in resolving power, pattern shape, LER, dry etching resistance, and stability over time.

[Examples 1F to 6F and Comparative Examples 1F to 5F (EUV)]
(Resist evaluation)
The negative resist solution shown in Table 14 prepared as described above was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and was heated on a hot plate at 100 ° C. for 60 seconds. Heat drying was performed to form a resist film having a thickness of 0.05 μm.
The obtained resist film was evaluated for sensitivity, resolving power, pattern shape, line edge roughness (LER), dry etching resistance, scum and stability over time by the following methods.

〔sensitivity〕
Using the EUV light (wavelength 13 nm) from an EUV exposure apparatus (Microexposure Tool manufactured by Exitech, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) on the obtained resist film The exposure was performed through a reflective mask having a 1: 1 line and space pattern with a line width of 100 nm while changing by 0.1 mJ / cm ^{2 in} the range of 0 to 20.0 mJ / cm ² , and then at 110 ° C. Baked for 2 seconds. Then, it developed using the 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution.
The exposure amount for reproducing a line and space (L / S = 1/1) mask pattern having a line width of 100 nm was defined as sensitivity. The smaller this value, the higher the sensitivity.

[Resolution]
The resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces (line: space = 1: 1) were separated and resolved) at the exposure amount showing the above sensitivity.

[Pattern shape]
The cross-sectional shape of a line pattern (L / S = 1/1) having a line width of 100 nm at the exposure amount showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). In the cross-sectional shape of the line pattern, a ratio represented by [line width at the top part (surface part) of the line pattern / line width at the middle part of the line pattern (a half height position of the line pattern)] is 1. Evaluation with 5 or more as “reverse taper”, ratio with 1.2 or more and less than 1.5 as “slightly reverse taper”, and ratio with less than 1.2 as “rectangular” It was.

[Line edge roughness (LER)]
A line pattern (L / S = 1/1) having a line width of 100 nm was formed with the exposure amount showing the above sensitivity. And about the arbitrary 30 points | pieces in the length direction 50 micrometers, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. A smaller value indicates better performance.

[Dry etching resistance]
A resist film formed by irradiating the entire surface with an exposure amount exhibiting the above sensitivity is HITACHI U-621 using Ar / C ₄ F ₆ / O ₂ gas (mixed gas with a volume ratio of 100/4/2). Dry etching was performed for 15 seconds. Thereafter, the resist remaining film ratio was measured and used as an index of dry etching resistance.
Very good: remaining film rate of 95% or more Good: less than 95% 90% or more Poor: less than 90%

[Scum evaluation]
A line pattern was formed by the same method as in the above [Pattern shape]. Thereafter, a cross-sectional SEM was obtained by S4800 (manufactured by Hitachi High-Tech Co., Ltd.), and the residue in the space portion was observed and evaluated as follows.
X: Scum is seen and patterns are partially connected.
○: Scum is seen but the patterns are not connected.
A: Scum is not seen.

[Stability over time]
After each composition was stored at room temperature for 1 month, the degree of change in sensitivity before and after storage (sensitivity measured in the above [sensitivity]) was evaluated. This evaluation was performed based on the following criteria.
(Criteria)
○ (Good): when the change in sensitivity is less than ^{1mJ / cm 2 △ (Fair)} : variation in sensitivity 1 mJ / cm ² or more, and, 3 mJ / cm ² or less which was a case × (Insufficient): Sensitivity When the fluctuation was greater than 3 mJ / cm ² .

  The above evaluation results are shown in Table 14.

As is apparent from the results shown in Table 14, Comparative Example 1F not using an acid proliferating agent, and Comparative Examples 2F to 5F using an acid proliferating agent not satisfying the general formula (I) are sensitivity, resolution, pattern shape, It turns out that it is inferior to LER and dry etching tolerance. Moreover, it turns out that scum reduction is also inferior about Comparative Example 1F, 4F, 5F, and stability with time is also inferior about Comparative Examples 2F-5F.
On the other hand, it can be seen that Examples 1F to 6F using the acid proliferating agent satisfying the general formula (I) are particularly excellent in sensitivity and scum reduction, and excellent in resolving power, pattern shape, LER, dry etching resistance, and stability over time.

Claims (17)

(A) A chemically amplified resist composition comprising a compound represented by the following general formula (I), and (B) a compound that generates an acid upon irradiation with actinic rays or radiation, wherein the compound (A) is A chemically amplified resist composition that is a compound that generates an acid having a volume of 200 ³ or more.

In the general formula (I), each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group. (A) a compound represented by the following general formula (I), (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a group that decomposes by the action of an acid to generate an alkali-soluble group. A chemically amplified resist composition for forming a positive pattern containing a resin having a resin, wherein the resin (C) is a resin having a repeating unit represented by the following formula (a) Composition.

In the general formula (I), each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group.

Decomposing by the action of an acid before Symbol resin (C), a group generate an alkali-soluble group is a group obtained by substituting an acetal group in which a hydrogen atom of the alkali-soluble group, a chemically amplified resist composition according to claim 2 object. Before SL resin (C) is a resin having a repeating unit represented by the following general formula (A), a chemical amplification type resist composition according to claim 2.

In the formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Ar ₁ represents an alkylene group or an aromatic ring group. R ₀₃ is an alkylene group, and may combine with the Ar ₁ as an aromatic ring group to form a ring together with the —C—C— chain.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4. The chemically amplified resist composition according to claim 4 , wherein the group capable of leaving by the action of an acid as Y in the general formula (A) has a structure represented by the following general formula (B).

In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group, a cycloaliphatic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. In addition, these cycloaliphatic groups and aromatic ring groups may contain a hetero atom.
In addition, at least two of Q, M, and L ₁ may be bonded to each other to form a 5-membered or 6-membered ring. Decomposing by the action of the acid, the resin having a group which produce an alkali-soluble group (C) is a resin having a repeating unit represented by the following general formula (2), in any one of claims 2-5 The chemically amplified resist composition as described.

In the general formula (2), R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring. (A) A compound represented by the following general formula (I), (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (D) a negative pattern forming material containing a crosslinking agent. Chemically amplified resist composition.

In the general formula (I), each of R _{1 to} R ₅ represents a hydrogen atom or a substituent. Two or more of R _{1 to} R ₅ may be bonded to each other to form a ring. R ₆ represents a substituent.
A represents a monovalent organic group.   The chemically amplified resist composition according to claim 7, wherein the crosslinking agent (D) is a compound having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule.   The chemical amplification resist composition according to claim 7 or 8, further comprising (E) a compound having a phenolic hydroxyl group. The chemically amplified resist composition according to claim 9, wherein the compound (E) having a phenolic hydroxyl group is a polymer compound having a repeating unit represented by the following general formula (2).

In the general formula (2), R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring.   The chemically amplified resist composition according to any one of claims 1 to 10, which is used for electron beam or extreme ultraviolet exposure. The chemically amplified resist composition according to any one of claims 1 to 11, wherein the compound (B) is a compound that generates an acid having a volume of 200 ³ or more upon irradiation with actinic rays or radiation. .   The resist film formed with the chemically amplified resist composition of any one of Claims 1-12.   A resist-coated mask blank coated with the resist film according to claim 13.   A method for forming a resist pattern, comprising exposing the resist film according to claim 13 and developing the exposed film.   A resist pattern forming method comprising exposing the resist-coated mask blank according to claim 14 and developing the exposed mask blank.   An electronic device manufacturing method including the resist pattern forming method according to claim 15.