JP5530645B2 - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon reaction with actinic rays or radiation, and a pattern forming method using the same. More specifically, semiconductor manufacturing processes such as IC, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes, lithographic printing plates, and actinic ray sensitive or radiation sensitive materials used in acid curable compositions. The present invention relates to a resin composition and a pattern forming method using the same.

The chemically amplified resist generates an acid in the exposed part by irradiation with radiation such as deep ultraviolet light, and the reaction using this acid as a catalyst changes the solubility of the active radiation irradiated part and the non-irradiated part in the developer, A pattern is formed on the substrate.
When a KrF excimer laser is used as an exposure light source, it is mainly composed of a resin having a basic skeleton of poly (hydroxystyrene), which has a small absorption in the 248 nm region. It 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, ArF excimer laser (193 nm) is used as the exposure light source, the chemical amplification system is not sufficient because the aromatic compound essentially shows a large absorption in the 193 nm region. .
For this reason, various ArF excimer laser resists containing an alicyclic hydrocarbon structure have been developed. However, from the viewpoint of overall performance as a resist, it is actually difficult to find an appropriate combination of resin, photoacid generator, additive, solvent, etc. to be used, and the line width is 100 nm or less. When such a fine pattern is formed, improvement in line edge roughness performance and resolution of the line pattern has been demanded.
It has been found that the line edge roughness performance is improved by incorporating a repeating unit having a specific lactone structure into the resin having the alicyclic hydrocarbon structure. For example, Patent Document 1 describes a resist composition using a resin containing a repeating unit having a spacer-type norbornane skeleton. Patent Document 2 describes a resist composition using a resin containing a repeating unit having a cyano group and a norbornane skeleton.
However, from the viewpoint of the overall performance as a resist, there is a demand for suppression of pattern variation (defocus latitude: DOF) caused by variation in the focal position during exposure and reduction of development defects.

JP 2005-352466 A JP 2007-156450 A

  The problem to be solved by the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition with improved DOF and development defects and a pattern forming method using the same.

一般式（Ａ）に於いて、
Ｘａ _１ は、水素原子、メチル基、トリフルオロメチル基又はヒドロキシメチル基を表す。
Ｔは、単結合又は２価の連結基を表す。
Ｒｘ _１ 〜Ｒｘ _３ は、それぞれ独立に、アルキル基又はシクロアルキル基を表す。
Ｒｘ _１ 〜Ｒｘ _３ の２つが結合して、シクロアルキル基を形成してもよい。

一般式（１’）に於いて、
Ｒ_２は、複数個ある場合にはそれぞれ独立に、置換基を有していてもよい鎖状または環状アルキレン基を表す。
Ｒ_３は、複数個ある場合にはそれぞれ独立に、置換基を有していてもよいアルキル基または置換基を有していてもよいシクロアルキル基を表し、複数個ある場合には２つのＲ_３が結合し、環を形成していても良い。
Ｘは、置換基を有していてもよいアルキレン基、酸素原子または硫黄原子を表す。
Ｙは、電子求引性基を表す。
Ｚは、複数個ある場合にはそれぞれ独立に、単結合、エーテル結合、エステル結合、アミド結合、ウレタン結合またはウレア結合を表す。
ｋは、置換基数であって、０〜８の整数を表す。
ｎは、繰り返し数を表し、１〜５の整数を表す。
＜２＞
（Ａ）成分の樹脂が、前記一般式（１’）で表されるラクトン構造を有する基とは異なるラクトン構造を有する基を含有する繰り返し単位を更に有する、＜１＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜３＞
（Ａ）成分の樹脂が、芳香族基を有さない、＜１＞又は＜２＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜４＞
（Ａ）成分の樹脂が、フッ素原子及び珪素原子を有さない、＜１＞〜＜３＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜５＞
フッ素原子及び珪素原子の少なくともいずれかを有する疎水性樹脂（ＨＲ）を更に含有し、前記疎水性樹脂（ＨＲ）の含有量が、組成物中の全固形分を基準として、０．１〜１０質量％である、＜１＞〜＜４＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜６＞
前記疎水性樹脂（ＨＲ）が下記一般式（Ｆ４）で表される繰り返し単位を含有する、＜５＞に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（Ｆ４）中、
Ｒ_６５〜Ｒ_６８は、それぞれ独立に、水素原子、フッ素原子又はアルキル基を表す。但し、Ｒ_６５〜Ｒ_６８の内、少なくとも１つは、フッ素原子又は少なくとも１つの水素原子がフッ素原子で置換されたアルキル基を表す。
＜７＞
前記疎水性樹脂（ＨＲ）が下記（ｘ）〜（ｚ）の群から選ばれる基を少なくとも１つを更に有する、＜５＞又は＜６＞に記載の感活性光線性又は感放射線性樹脂組成物。
（ｘ）アルカリ可溶性基、
（ｙ）アルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基、
（ｚ）酸の作用により分解する基
＜８＞
（Ａ）下記一般式（Ａ）で表される繰り返し単位を２種有し、下記一般式（１）で表される基を有する繰り返し単位を有し、酸の作用によりアルカリ現像液に対する溶解度が増大する樹脂及び（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を含有し、組成物中の全固形分濃度が１〜１０質量％の感活性光線性又は感放射線性樹脂組成物。

一般式（Ａ）に於いて、
Ｘａ _１ は、水素原子、メチル基、トリフルオロメチル基又はヒドロキシメチル基を表す。
Ｔは、単結合又は２価の連結基を表す。
Ｒｘ _１ 〜Ｒｘ _３ は、それぞれ独立に、アルキル基又はシクロアルキル基を表す。
Ｒｘ _１ 〜Ｒｘ _３ の２つが結合して、シクロアルキル基を形成してもよい。

一般式（１）に於いて、
Ｒ_２は、複数個ある場合にはそれぞれ独立に、置換基を有していてもよい鎖状または環状アルキレン基を表す。
Ｒ_３は、複数個ある場合にはそれぞれ独立に、置換基を有していてもよいアルキル基または置換基を有していてもよいシクロアルキル基を表し、複数個ある場合には２つのＲ_３が結合し、環を形成していても良い。
Ｘは、置換基を有していてもよいアルキレン基、酸素原子または硫黄原子を表す。
Ｙは、複数個ある場合にはそれぞれ独立に、シアノ基、ニトロ基、カルボキシル基、又はアルキルスルホニル基のいずれかである電子求引性基を表す。
Ｚは、複数個ある場合にはそれぞれ独立に、単結合、エーテル結合、エステル結合、アミド結合、ウレタン結合またはウレア結合を表す。
ｋは、置換基数であって、０〜８の整数を表す。
ｎは、繰り返し数を表し、１〜５の整数を表す。
ｍは、置換基数であって、１〜７の整数を表す。
＜９＞
（Ａ）成分の樹脂が、下記一般式（２）で表される繰り返し単位を有することを特徴とする＜８＞に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（２）に於いて、
Ｒ_１は、水素原子、置換基を有していてもよいアルキル基またはハロゲン原子を表す。
Ｒ_２は、複数個ある場合にはそれぞれ独立に、置換基を有していてもよい鎖状または環状アルキレン基を表す。
Ｒ_３は、複数個ある場合にはそれぞれ独立に、置換基を有していてもよいアルキル基または置換基を有していてもよいシクロアルキル基を表し、複数個ある場合には２つのＲ_３が結合し、環を形成していても良い。
Ｘは、置換基を有していてもよいアルキレン基、酸素原子または硫黄原子を表す。
Ｙは、複数個ある場合にはそれぞれ独立に、電子求引性基を表す。
Ｚは、複数個ある場合にはそれぞれ独立に、単結合、エーテル結合、エステル結合、アミド結合、ウレタン結合またはウレア結合を表す。
ｋは、置換基数であって、０〜８の整数を表す。
ｎは、繰り返し数を表し、１〜５の整数を表す。
ｍは、置換基数であって、１〜７の整数を表す。
＜１０＞
（Ａ）成分の樹脂が、下記一般式（３）で表される繰り返し単位を有することを特徴とする＜８＞又は＜９＞に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（３）に於いて、
Ｒ_１ａは、水素原子または置換基を有していてもよいアルキル基を表す。
Ｒ_３は、複数個ある場合にはそれぞれ独立に、置換基を有していてもよいアルキル基または置換基を有していてもよいシクロアルキル基を表し、複数個ある場合には２つのＲ_３が結合し、環を形成していても良い。
Ｘは、置換基を有していてもよいアルキレン基、酸素原子または硫黄原子を表す。
ｋは、置換基数であって、０〜８の整数を表す。
ｌは、繰り返し数を表し、１〜５の整数を表す。
ｎは、繰り返し数を表し、１〜５の整数を表す。
ｍは、置換基数であって、１〜７の整数を表す。
＜１１＞
＜１＞〜＜１０＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物により、膜を形成し、該膜を露光、現像する工程を含むことを特徴とするパターン形成方法。
＜１２＞
＜１＞〜＜１０＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成されたレジスト膜。
本発明は、前記＜１＞〜＜１２＞に係る発明であるが、以下、それ以外の事項（例えば、下記（１）〜（４））についても記載している。 The present invention is as follows.
<1>
(A) It has two repeating units represented by the following general formula (A), has a repeating unit having a group represented by the following general formula (1 ′), and is soluble in an alkali developer by the action of an acid. An actinic ray-sensitive or radiation-sensitive resin composition containing a resin that increases the amount of acid and (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and having a total solid content in the composition of 1 to 10% by mass .

In general formula (A),
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 an alkyl group or a cycloalkyl group.
Two are bonded in rx ₁ to Rx _3, may form a cycloalkyl group.

In general formula (1 ′),
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; ₃ may combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group.
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.
<2>
The actinic ray according to <1>, wherein the resin of component (A) further has a repeating unit containing a group having a lactone structure different from the group having a lactone structure represented by the general formula (1 ′). Or radiation sensitive resin composition .
<3 >
The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2> , wherein the resin of component (A) does not have an aromatic group.
< 4 >
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to < 3 >, wherein the resin of component (A) does not have a fluorine atom or a silicon atom.
< 5 >
It further contains a hydrophobic resin (HR) having at least one of a fluorine atom and a silicon atom, and the content of the hydrophobic resin (HR) is 0.1 to 10 on the basis of the total solid content in the composition. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to < 4 >, which is% by mass.
< 6 >
The actinic ray-sensitive or radiation-sensitive resin composition according to < 5 >, wherein the hydrophobic resin (HR) contains a repeating unit represented by the following general formula (F4).

In general formula (F4),
R _{65 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{65 to} R ₆₈ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
< 7 >
The actinic ray-sensitive or radiation-sensitive resin composition according to < 5 > or < 6 >, wherein the hydrophobic resin (HR) further has at least one group selected from the following groups (x) to (z): object.
(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) Group < 8 > decomposing by the action of acid
(A) It has two repeating units represented by the following general formula (A), has a repeating unit having a group represented by the following general formula (1), and has a solubility in an alkali developer due to the action of an acid. An actinic ray-sensitive or radiation-sensitive resin composition containing an increasing resin and (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, wherein the total solid concentration in the composition is 1 to 10% by mass.

In general formula (A),
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 an alkyl group or a cycloalkyl group.
Two are bonded in rx ₁ to Rx _3, may form a cycloalkyl group.

In general formula (1),
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; ₃ may combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y, when there are a plurality of them, each independently represents an electron-withdrawing group that is one of a cyano group, a nitro group, a carboxyl group , and an alkylsulfonyl group .
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7 .
<9 >
The actinic ray-sensitive or radiation-sensitive resin composition according to < 8>, wherein the resin of component (A) has a repeating unit represented by the following general formula (2).

In general formula (2),
R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom.
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; ₃ may combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently when there are two or more.
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.
<1 0 >
The actinic ray-sensitive or radiation-sensitive resin composition according to < 8 > or <9> , wherein the resin of component (A) has a repeating unit represented by the following general formula (3).

In general formula (3),
R _1a represents a hydrogen atom or an alkyl group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; ₃ may combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
k is the number of substituents and represents an integer of 0 to 8.
l represents the number of repetitions and represents an integer of 1 to 5.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.
<1 1 >
<1>-<1 0 > The pattern characterized by including the process of forming a film | membrane with the actinic-ray-sensitive or radiation-sensitive resin composition of any one of <1>, and exposing and developing this film | membrane. Forming method.
<1 2 >
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <1 0 >.
The present invention is an invention according to the above <1> to <1 2 >, but hereinafter, other matters (for example, the following (1) to (4)) are also described.

(1) (A) a resin having a repeating unit having a group represented by the following general formula (1), which increases the solubility in an alkali developer by the action of an acid, and (B) an acid upon irradiation with actinic rays or radiation. An actinic ray-sensitive or radiation-sensitive resin composition, comprising a compound that generates odor.

In general formula (1),
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; _Three
May combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently when there are two or more.
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

  (2) The actinic ray-sensitive or radiation-sensitive resin composition according to (1), wherein the resin of component (A) has a repeating unit having a lactone structure represented by the following general formula (2) object.

In general formula (2),
R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom.
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; _Three
May combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently when there are two or more.
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

  (3) The actinic ray-sensitive or radiation-sensitive resin as described in (1) or (2) above, wherein the resin of component (A) has a repeating unit represented by the following general formula (3) Composition.

In general formula (3),
R _1a represents a hydrogen atom or an alkyl group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; _Three
May combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
k is the number of substituents and represents an integer of 0 to 8.
l represents the number of repetitions and represents an integer of 1 to 5.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

  (4) A step of forming a film with the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (3) above, and exposing and developing the film. Pattern forming method.

  According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition with improved DOF and development defects and a pattern forming method using the same. The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises a resin (so-called acid-decomposable resin) whose solubility in an alkaline developer is increased by the action of an acid and a compound that generates an acid upon irradiation with actinic rays or radiation. It is particularly suitable as a positive photosensitive composition such as a positive resist composition containing a so-called photoacid generator.

Hereinafter, the best mode for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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).

(A) having a repeating unit having a group having a lactone structure represented by the general formula (1),
Resin whose solubility in alkaline developer is increased by the action of acid The resin of component (A) is a resin whose solubility in alkaline developer is increased by the action of acid and has a lactone structure represented by the general formula (1). A group that has a repeating unit having a group and decomposes by the action of an acid on the main chain or side chain of the resin, or both the main chain and the side chain to generate an alkali-soluble group (hereinafter referred to as “acid-decomposable group” Resin) (acid-decomposable resin).
The resin of component (A) has a repeating unit having a group having a lactone structure represented by the following general formula (1).

In general formula (1),
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; _Three
May combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently when there are two or more.
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

The group represented by R ₂ is not particularly limited as long as it is a chain alkylene group or a cyclic alkylene group, but a preferable chain alkylene group is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably. Has 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. Preferable cyclic alkylene is C1-C20 cyclic alkylene, for example, cyclohexylene, cyclopentylene, norbornylene, adamantylene, etc. are mentioned. The group represented by R ₂ is preferably a chain alkylene, and particularly preferably a methylene group. The chain alkylene group and the cyclic alkylene group are not particularly limited and may have a substituent. Examples of the substituent on the chain alkylene group and cyclic alkylene group include, for example, halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, Alkoxy groups such as benzyloxy group, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, sec-butyl groups, t-butyl groups, pentyl groups, hexyl groups, etc., cyclopropyl, cyclobutyl, cyclopentyl, Examples thereof include cycloalkyl groups such as cyclohexyl group and cycloheptyl group, and cyano group, nitro group, sulfonyl group, silyl group, ester group, acyl group, vinyl group, aryl group and the like. When n is 2 or more, the groups represented by R ₂ may be independently the same or different.

The alkyl group represented by R ₃ preferably has 1 to 30 carbon atoms, more preferably a linear alkyl group or branched alkyl group having 1 to 15 carbon atoms. Specifically, a methyl group,
Linear alkyl group such as ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, isopropyl And branched alkyl groups such as an isobutyl group, a t-butyl group, a neopentyl group, and a 2-ethylhexyl group.
The cycloalkyl group as R ₃ is preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and may have an oxygen atom in the ring. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
The alkyl group and cycloalkyl group of R ₃ may have a substituent. Examples of the substituent on the alkyl group and cycloalkyl group include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, and benzyl. Alkoxy groups such as oxy groups, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, sec-butyl groups, t-butyl groups, pentyl groups, hexyl groups and other alkyl groups, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl Group, cycloalkyl group such as cycloheptyl group, and cyano group, nitro group, sulfonyl group, silyl group, ester group, acyl group, vinyl group, aryl group and the like. In the case where there are a plurality of groups, two R ₃ groups may be bonded to form a ring (preferably a cycloalkylene group).

  X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom. The alkylene group which may have a substituent is preferably an alkylene group having 1 to 2 carbon atoms, and examples thereof include a methylene group and an ethylene group. Examples of the substituent on the alkylene group include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group. Alkoxy groups such as alkoxy group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group, cycloheptyl And a cycloalkyl group such as a group, and a cyano group, a nitro group, a sulfonyl group, a silyl group, an ester group, an acyl group, a vinyl group, and an aryl group.

As the electron-withdrawing group Y, for example, a cyano group, a nitro group, a carboxyl group, halogenation alkyl group (preferably having 10 or less carbon atoms), alkoxycarbonyl groups (preferably 10 or less carbon atoms), an alkylsulfonyl group (Preferably having 10 or less carbon atoms ) . The good preferable Y, cyano group, nitro group, hydroxy group, halogenated alkyl group, particularly preferred Y, and a cyano group. The substitution position of Y is most preferably as follows.

  The group represented by Z includes a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, more preferably a single bond, an ether bond or an ester bond, particularly preferably. An ester bond. Z may be located on either the end side or the exo side of the norbornane skeleton.

  k is the number of substituents and represents an integer of 0 to 8, more preferably 0 to 5, and particularly preferably 0 to 3. n represents the number of repetitions, represents an integer of 1 to 5, more preferably 1 to 2, and most preferably 1. m is the number of substituents and represents an integer of 1 to 7. More preferably, it is 1-5, Most preferably, it is 1-3. Most preferably 1.

  The repeating unit having a group having a lactone structure represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2).

In general formula (2),
R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom.
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; _Three
May combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently when there are two or more.
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

In the general formula _{(2), R 2, R} 3, X, Y, Z, k, n, m are in the general formula _{(1), R 2, R} 3, X, Y, Z, k , N and m.
The alkyl group for R ₁ is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. The alkyl group may have a substituent. Preferred substituents on the alkyl group include a halogen atom, a hydroxyl group, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an alkoxy group such as a benzyloxy group, and the like. Particularly preferred groups as R ₁ are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group.

  The repeating unit having a group having a lactone structure represented by the general formula (1) is more preferably a repeating unit represented by the following general formula (3).

In general formula (3),
R _1a represents a hydrogen atom or an alkyl group which may have a substituent.
When R _1a is an alkyl group (preferably having a carbon number of 1 to 10), it may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and a hydroxy group. It is done.
R _1a is preferably an unsubstituted methyl group.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; _Three
May combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
k is the number of substituents and represents an integer of 0 to 8.
l represents the number of repetitions and represents an integer of 1 to 5.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

In the general formula (3), R ₃ , X, k, n and m are the same as R ₃ , X,
It is synonymous with k, n, m.
The halogenated methyl group for R _1a is preferably a trifluoromethyl group.
Particularly preferred groups for R _1a are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group.
l is the number of repeating methylene groups and represents an integer of 1 to 5, more preferably an integer of 1 to 3. Particularly preferred is 1.

The content of the repeating unit having a group having a lactone structure represented by the general formula (1) is preferably 15 to 70 mol%, more preferably 20 to 50 mol%, still more preferably based on all repeating units in the polymer. 30 to 50 mol%.
The repeating unit having a group having a lactone structure is a molar ratio of acid-decomposable repeating units (
The range of ± 20 mol% of (mol%) is particularly preferred from the viewpoint of developability.

The method for synthesizing the compound represented by the general formula (1) is not particularly limited, but can be synthesized using the following method.
That is, after synthesizing norbornene (a) by Diels-Alder reaction from the corresponding diene and dienophile, (1) (b) is obtained via halolactonization or epoxide using the double bond site as a foothold.
The spacer site R ₂ and the polymerizable site A are (2) etherification reaction of the spacer site,
After introduction by an esterification reaction, etc., it may be introduced stepwise by introducing a polymerizable site, or (4) units having both a polysynthetic site and a spacer site may be directly linked.

  R in the formula (a) represents, for example, a hydrogen atom, an alkyl group, or an aryl group, and is preferably an alkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. .

  Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (1) are shown below, but the present invention is not limited thereto.

In the following specific examples, R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group or a halogen atom. Represent.

  The repeating unit containing a group having a lactone structure represented by the general formula (1) includes (meth) acrylic acid ester derivatives, (meth) acrylamide derivatives, vinyl ether derivatives, olefin derivatives having the structure of the general formula (1) , Repeating units having a styrene derivative, and the like, preferably a repeating unit having a (meth) acrylic acid ester derivative having the structure of the general formula (1).

  In addition to the repeating unit containing the group having the lactone structure represented by the general formula (1), the resin of the component (A) is further different from the group having the lactone structure represented by the general formula (1). You may have a repeating unit containing group which has. Any lactone structure can be used as long as it has a lactone structure, but a 5- to 7-membered lactone structure is preferable, and a bicyclo structure or a spiro structure is formed in the 5- to 7-membered ring lactone structure. The other ring structure is preferably condensed. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14). Edge roughness and development defects are improved.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

  Examples of the repeating unit having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-17) include a repeating unit represented by the following general formula (AI).

In general formula (AI),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 4 carbon atoms). Preferred substituents that the alkyl group represented by Rb ₀ may have 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 a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. Preferably a single bond, -Ab ₁ -CO ₂ - is a divalent linking group represented by. Ab ₁
Is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group having a structure 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 (ee) thereof is preferably 90 or more, more preferably 95 or more.

  The content of the repeating unit having a group having another lactone structure is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, still more preferably from 30 to 50 mol%, based on all repeating units in the polymer.

  Specific examples of the repeating unit having a group having another lactone structure are listed below, but the present invention is not limited thereto.

  Examples of the repeating unit having a group having a particularly preferable lactone structure include the following repeating units. By selecting an optimal lactone group, the pattern profile and the density dependence become good.

The resin of component (A) is a resin whose solubility in an alkaline developer is increased by the action of an acid, and decomposes into the main chain or side chain of the resin or both the main chain and the side chain by the action of an acid, It is a resin having a group that generates an alkali-soluble group (acid-decomposable group).
Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
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.
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.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

  The resin of component (A) preferably has a repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following general formula (A).

In general formula (A),
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 an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.
The alkyl group of Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred. Of these, preferred groups include a cyclopentyl group and a cyclohexyl group.
Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, A polycyclic cycloalkyl group such as an adamantyl group is preferred.
It is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group, particularly a cyclopentyl group or a cyclohexyl group.
It is also preferred that Rx ₁ and Rx ₂ are alkyl groups and Rx ₃ is a cycloalkyl group.

  As for content of the repeating unit which has an acid-decomposable group, 20-50 mol% is preferable with respect to all the repeating units in a polymer, More preferably, it is 25-45 mol%.

  Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this.

  The resin of component (A) preferably has a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

In general formulas (VIIa) to (VIIc),
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. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the remaining are hydrogen atoms.

Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ (VIIc), same meanings as R ₂ c~R ₄ c.

  The content of the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 with respect to all repeating units in the polymer. ˜25 mol%.

  Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

  The resin of component (A) preferably has a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the α-position. It is more preferable to have a repeating unit. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  As for content of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in a polymer, More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.

  Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.

The resin of component (A) may further have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low molecular components from the resist film to the immersion liquid during immersion exposure. Examples of such a repeating unit include 1-adamantyl (meth) acrylate, diamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and cyclohexyl (meth) acrylate repeating units.
Specific examples of the repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability are given below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  In addition to the above repeating structural unit, the resin of component (A) includes dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, such as resolution, heat resistance, and sensitivity. Various repeating structural units can be included for the purpose of adjusting the above.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, the performance required for the resin of component (A), in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin of component (A), the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance required for resolving power and heat resistance. In order to adjust the sensitivity and the like, it is set as appropriate.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure, the resin of component (A) preferably has no aromatic group from the viewpoint of transparency to ArF light.
Moreover, it is preferable that the resin (A) of this invention does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin (HR) mentioned later.

The resin of component (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the composition of the present invention such as propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol), and cyclohexanone described later is dissolved. Solvent to be used. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction (the concentration of the solute in the reaction solution) is usually 5 to 50% by mass, preferably 10 to 30% by mass.
The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

The weight average molecular weight of the component (A) resin is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and still more preferably 3,000 as a polystyrene-converted value by the GPC method. ˜15,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
The degree of dispersion (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 1.7. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the blending amount of the component (A) resin in the entire composition is preferably 50 to 99.9% by mass, more preferably 60%, based on the total solid content.
˜99.0% by mass.
In the present invention, the resin of component (A) may be used alone or in combination.

(B) Compound that generates acid upon irradiation with actinic ray or radiation The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound that generates an acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generator”). ").
As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro resist Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407. JP, 63-26653, JP, 55-164824, JP, 62-69263, JP, 63-146038, JP, 63-163452, JP, 62-153853, The compounds described in JP-A 63-146029 can be used.

Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

  Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In general formula (ZI):
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1
~ 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

  Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as methyl. Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group and the like.

  The aromatic group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), aryl Ruoxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.

  Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, and the like.

  The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom and alkyl as in the aromatic sulfonate anion Group, cycloalkyl group, alkoxy group, alkylthio group and the like.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Alkyl groups substituted with fluorine atoms are preferred.

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group. A bis (alkylsulfonyl) imide anion substituted with a fluorine atom and a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or R ₂₀₁
Some of to R ₂₀₃ is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. An alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom and a sulfur atom. , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 8 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c , such as a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxy group. A carbonylmethyl group is more preferred.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as in R _{1c to} R _5c .

R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like.

The alkyl group and cycloalkyl group in R ₂₀₄ to R _207, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

  Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.
Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates monovalent perfluoroalkanesulfonic acid, or a monovalent fluorine atom or fluorine atom. A compound that generates an aromatic sulfonic acid substituted with a group containing fluorinated acid, or a compound that generates a monovalent fluorine atom or imide acid substituted with a group containing a fluorine atom, and even more preferably, It is a sulfonium salt of a substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imide acid or a fluorine-substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid or a fluorinated substituted imido acid whose pKa of the generated acid is pKa = -1 or less, and the sensitivity is improved. .

  Among acid generators, particularly preferred examples are listed below, but the present invention is not limited thereto.

  Among these, preferred acid generators are a fluorinated substituted alkanesulfonic acid having at least one substituent and a fluorine-substituted imidic acid having at least one substituent, and particularly preferred are a sulfonamide group or a sulfonic acid. Fluorinated substituted alkanesulfonic acid having at least one ester group and fluorinated imidic acid, and specific examples include z66, z67, z68, z69, z70, z72, z73, z78, z88 and z90.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 20% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, and more Preferably it is 0.5-10 mass%, More preferably, it is 1-7 mass%.

Solvent Examples of the solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid Alkyl esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may contain rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, etc. The organic solvent can be mentioned.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3- Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methyl Preferred is cycloheptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned.
In the present invention, the above solvents may be used alone or in combination of two or more.

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.
Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate. 2-heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

  The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

Basic Compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) to (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
The alkyl groups in these general formulas (A) to (E) are more preferably unsubstituted.

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undecar 7-ene etc. are mentioned. Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris ( and t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. As the compound having an onium carboxylate structure, an anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably 6 to 1 carbon atoms
2) may be bonded to a nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.
Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, chloride, bromide, and iodide are particularly preferable. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.
It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

In the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group, the sulfonic acid ester group may be any of alkyl sulfonic acid ester, cycloalkyl group sulfonic acid ester, and aryl sulfonic acid ester. In the case of an alkyl sulfonate ester, the alkyl group has 1 to 20 carbon atoms, in the case of a cycloalkyl sulfonate ester, the cycloalkyl group has 3 to 20 carbon atoms, and in the case of an aryl sulfonate ester, the aryl group has 6 carbon atoms. ~ 12 are preferred. Alkyl sulfonic acid ester, cycloalkyl sulfonic acid ester, and aryl sulfonic acid ester may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, and a sulfonic acid. An ester group is preferred.
It is preferable to have at least one oxyalkylene group between the sulfonate group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  These basic compounds are used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of actinic-ray-sensitive or radiation-sensitive resin composition, Preferably it is 0.01-5 mass%.

  The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

Surfactant The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a surfactant, and is a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based interface). It is more preferable to contain any one or two or more of an activator and a surfactant having both a fluorine atom and a silicon atom.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains the above-mentioned surfactant, adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It is possible to provide a resist pattern with less.
Examples of the fluorine-based and / or silicon-based surfactant include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Surfactant can be mentioned, The following commercially available surfactant can also be used as it is.
Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.),
Megafuck F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink and Chemicals), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass ( Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toagosei Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, 352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208, 230G, 204 , Mention may be made of 208D, 212D, 218D, the fluorine-based surfactant or silicone-based surfactants such as 222D ((KK) Neos). Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₃ F ₇ group and (poly (oxy) And a copolymer of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

  In the present invention, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Sorbitans such as polyoxyethylene alkyl aryl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopa Mite - DOO, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, may be mentioned polyoxyethylene sorbitan tristearate nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as such.

  These surfactants may be used alone or in several combinations.

  The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). is there.

Carboxylic acid onium salt The actinic ray-sensitive or radiation-sensitive resin composition in 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, as the carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. Furthermore, it is preferable that the carboxylate residue of the carboxylic acid onium salt of the present invention does not contain an aromatic group or a carbon-carbon double bond. As a particularly preferable anion moiety, a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. 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.

  Fluorine-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, 2 , 2-bistrifluoromethylpropionic acid anion and the like.

  These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

  The content of the carboxylic acid onium salt in the composition is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, based on the total solid content of the composition. %.

Dissolution-inhibiting compound having a molecular weight of 3000 or less that decomposes by the action of an acid to increase the solubility in an alkali developer. Dissolution-inhibiting compound having a molecular weight of 3000 or less that decomposes by the action of an acid to increase the solubility in an alkali developer. (Hereinafter also referred to as “dissolution-inhibiting compound”), since it does not lower the permeability of 220 nm or less, like cholic acid derivatives containing acid-decomposable groups described in Proceeding of SPIE, 2724,355 (1996). An alicyclic or aliphatic compound containing an acid-decomposable group is preferred. Examples of the acid-decomposable group and alicyclic structure are the same as those described for the component (A) resin.

  When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, it contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. Those are preferred. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.

  The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

  The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

  Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

Other Additives In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a compound that further promotes solubility in dyes, plasticizers, photosensitizers, light absorbers, and developers as necessary. (For example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) and the like can be contained.

Such phenolic compounds having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

Pattern Forming Method The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used at a film thickness of 30 to 250 nm, more preferably at a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. It is preferable. By setting the solid content concentration in the actinic ray-sensitive or radiation-sensitive resin composition to an appropriate range to have an appropriate viscosity, and improving the coating property and film forming property, such a film thickness is obtained. Can do.
The total solid concentration in the actinic ray-sensitive or radiation-sensitive resin composition is generally 1 to 10% by mass, more preferably 1 to 8.0% by mass, and still more preferably 1.0 to 6.0. % By mass.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is prepared by dissolving the above-described components in a predetermined organic solvent, preferably the mixed solvent, filtered, and applied onto a predetermined support as follows. And use. The filter used for filter filtration is preferably made of polytetrafluoroethylene, polyethylene, or nylon of 0.1 microns or less, more preferably 0.05 microns or less, and still more preferably 0.03 microns or less.

For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater. Dry to form a resist film.
The resist film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, etc., preferably 250 nm or less, more preferably 220 nm or less, particularly preferably 1 to 1. Far ultraviolet light having a wavelength of 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc. ArF excimer laser, F ₂ Excimer laser, EUV (13 nm), and electron beam are preferable.

Before forming the resist film, an antireflection film may be coated on the substrate in advance.
As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

In the development step, an alkaline developer is used as follows. Examples of the alkali developer for the actinic ray-sensitive or radiation-sensitive resin composition include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, and n-propyl. Primary amines such as amines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxy Alkaline aqueous solutions such as quaternary ammonium salts such as tetraethylammonium hydroxide and cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.
As the rinsing liquid, pure water can be used, and an appropriate amount of a surfactant can be added.
Further, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is exposed by filling a liquid (immersion medium) having a refractive index higher than air between the resist film and the lens when irradiated with actinic rays or radiation. It can also be suitably used for pattern formation by immersion exposure. Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.

The immersion liquid used for the immersion exposure will be described below.
The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the resist film. Is an ArF excimer laser (wavelength; 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-mentioned viewpoints.
Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, the surface tension of the water is decreased and the surface activity is increased, so that the resist film on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element can be ignored. An additive (liquid) may be added in a small proportion. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained. On the other hand, when an opaque material or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light, the optical image projected on the resist film is distorted. . Further, pure water filtered through an ion exchange filter or the like may be used.

The electrical resistance of water as the immersion liquid is preferably 18.3 MQcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

When the resist film comprising the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is exposed through an immersion medium, a hydrophobic resin (HR) can be further added as necessary. As a result, hydrophobic resin (HR) is unevenly distributed on the surface of the resist film, and when the immersion medium is water, the receding contact angle of the resist film surface with respect to the water when the resist film is formed is improved, and the immersion water tracking is improved. Can be made. As the hydrophobic resin (HR), any resin can be used as long as the receding contact angle of the surface can be improved by addition, but a resin having at least one of fluorine atom and silicon atom is preferable. The receding contact angle of the resist film is preferably 60 ° to 90 °, more preferably 70 ° or more. The addition amount can be adjusted as appropriate so that the receding contact angle of the resist film falls within the above range, but is 0.1 to 10% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is preferable that it is 0.1-5 mass% more preferably. Hydrophobic resin (HR) is ubiquitous at the interface as described above, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances are mixed uniformly. There is no need to contribute.
The receding contact angle is the contact angle measured when the contact line at the droplet-substrate interface recedes,
It is generally known to be useful in simulating the ease with which a droplet moves in a dynamic state. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.
In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  The fluorine atom or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be substituted on the side chain.

The hydrophobic resin (HR) is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The present invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{57 to} R ₆₁ , R _{62 to} R ₆₄ and R _{65 to} R ₆₈ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably having a carbon number of 1 ~ 4). R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 1,3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.

Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .
X ₂ represents —F or —CF ₃ .

The hydrophobic resin (HR) is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. As the divalent linking group, an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a ureylene group is used alone or in combination of two or more groups. A combination is mentioned.
n represents an integer of 1 to 5.

Hereinafter, although the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Furthermore, the hydrophobic resin (HR) may have at least one group selected from the following groups (x) to (z).
(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) A group that decomposes by the action of an acid.

(X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.
Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

Examples of the repeating unit having an alkali-soluble group (x) include a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a main group of the resin via a linking group. Examples include repeating units in which an alkali-soluble group is bonded to the chain. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain. Is also preferable.
The content of the repeating unit having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the polymer.

  Specific examples of the repeating unit having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto.

(Y) Examples of the group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer include a group having a lactone structure, an acid anhydride group, an acid imide group, and the like, and preferably a lactone A group having a structure.
Group (y) which decomposes by the action of an alkali developer and increases the solubility in the alkali developer
As the repeating unit having a group (y), which is decomposed by the action of an alkali developer on the main chain of the resin and increases the solubility in the alkali developer, such as a repeating unit of an acrylic ester or a methacrylic ester. It is preferable to use a polymerization initiator or a chain transfer agent having a repeating unit that is bonded or a group (y) that increases the solubility in an alkaline developer at the end of the polymer chain during polymerization.
The content of the repeating unit having a group (y) that decomposes by the action of the alkali developer and increases the solubility in the alkali developer is preferably from 1 to 40 mol%, more preferably, based on all repeating units in the polymer. Is 3 to 30 mol%, more preferably 5 to 15 mol%.

  Specific examples of the repeating unit having a group (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer are the same as those of the repeating unit having a lactone structure exemplified for the resin of component (A) Can be mentioned.

  In the hydrophobic resin (HR), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group listed for the resin of the component (A). . In the hydrophobic resin (HR), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 10%, based on all repeating units in the polymer. 80 mol%, more preferably 20 to 60 mol%.

  The hydrophobic resin (HR) may further have a repeating unit represented by the following general formula (III).

In general formula (III):
R ₄ represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group.
L ₆ represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R ₄ is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The divalent linking group of L ₆ is preferably an alkylene group (preferably having 1 to 5 carbon atoms) or an oxy group.

When the hydrophobic resin (HR) has a fluorine atom, the fluorine atom content is determined by the hydrophobic resin (
It is preferable that it is 5-80 mass% with respect to the molecular weight of HR), and it is more preferable that it is 10-80 mass%. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% in hydrophobic resin (HR), and it is more preferable that it is 30-100 mass%.
When the hydrophobic resin (HR) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass and preferably 2 to 30% by mass with respect to the molecular weight of the hydrophobic resin (HR). Is more preferable. Moreover, it is preferable that it is 10-100 mass% in hydrophobic resin (HR), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-100 mass%.

  The weight average molecular weight of the hydrophobic resin (HR) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 15,000. is there.

  The hydrophobic resin (HR), like the resin of the component (A), naturally has few impurities such as metals, and the residual monomer and oligomer components are preferably 0 to 10% by mass, more preferably. Is more preferably 0 to 5% by mass and 0 to 1% by mass. Thereby, a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

  As the hydrophobic resin (HR), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. The concentration of the reaction (the concentration of the solute in the reaction solution) is usually 5 to 50% by mass, preferably 30 to 50% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

  The resin may be once deposited and separated, and then dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

  Specific examples of the hydrophobic resin (HR) are shown below. Table 1 below shows the molar ratio of the repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

In order to prevent the resist film from directly contacting the immersion liquid between the resist film and the immersion liquid of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, an immersion liquid hardly soluble film (hereinafter, (Also referred to as “top coat”). The necessary functions for the top coat are suitability for application to the upper layer of the resist, radiation, especially transparency to 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the resist upper layer.
From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples thereof include a polymer and a fluorine-containing polymer. The aforementioned hydrophobic resin (HR) is also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having a small penetration into the resist film is preferable. It is preferable that the peeling process can be performed with an alkali developer in that the peeling process can be performed simultaneously with the resist film development process. From the viewpoint of peeling with an alkaline developer, the topcoat is preferably acidic, but may be neutral or alkaline from the viewpoint of non-intermixability with the resist film.
The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. In the case of using water as the immersion liquid in an ArF excimer laser (wavelength: 193 nm), the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

  The top coat is preferably not mixed with the resist film and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is a poorly soluble and non-water-soluble medium in the solvent used for the actinic ray-sensitive or radiation-sensitive resin composition. It is preferable that Furthermore, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

Synthesis Example 1 (Synthesis of Compound (3))
The following compound (1) was synthesized by the method described in International Publication No. 07/037213 pamphlet.
Compound (1) (120 g, 0.67 mol) and pyridine (64 g, 0.8 mol) are dissolved in 750 ml of THF in a 3 L three-necked flask, and then the internal temperature of chloroacetyl chloride (113 g, 1 mol) is lowered while cooling in an ice bath. The solution was added dropwise while maintaining the temperature at 15 ° C or lower. After completion of dripping, keep cooling in ice bath 30
After stirring for 5 minutes, it was removed from the ice bath and stirred for another 4 hours at room temperature. The three-necked flask was cooled again in an ice bath, and then 1.5 L of water was added dropwise while maintaining the internal temperature at 15 ° C. or lower, and ethyl acetate was further added. The purified crude crystals were collected by filtration, further extracted from the filtrate, and the organic layer was concentrated to obtain crude crystals. These crude crystals were combined, dissolved again in ethyl acetate, washed twice with saturated aqueous sodium bicarbonate, and concentrated to obtain the following compound (2) (165 g).
Compound (2) (165 g, 0.65 mol) was dissolved in 750 ml of NMP in a 3 L three-necked flask, and then methacrylic acid (63.7 g, 0.74 mol) and potassium carbonate (138 g, 1 mol) were added at room temperature. Next, after cooling in an ice bath, potassium iodide (47 g, 0.28 mol) was added and stirred for 1 hour, and further stirred at room temperature for 5 hours. While the reaction vessel was cooled again in an ice bath, hydrochloric acid was added to adjust the reaction solution to a pH of about 2, and extraction was performed using ethyl acetate. The organic layer was washed with sodium bicarbonate water and saturated brine, decolorized with activated carbon, and concentrated. When the obtained crude product was allowed to stand at room temperature for 12 hours, crude crystals were precipitated. The obtained crude crystals were purified by filtration after stirring in methanol to obtain the following compound (3) (122 g).
1H NMR spectrum (CDCl ₃ )
σ (ppm): 6.23 (1H, q), 5.70 (1H, q), 4.69-4.66 (4H, m), 3.62-3.59 (1H, m), 2.76 (1H,
m), 2.40 (1H, dd), 2.25 (1H, dd), 2.16 (1H, ddd), 1.98 (3H, dd), 1.96 (1H, m)

Synthesis Example 2 (Synthesis of polymer (1))
Under a nitrogen stream, 41 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. A solution in which 9.77 g, 2.02 g, 7.29 g, a polymerization initiator V601 (manufactured by Wako Pure Chemical Industries, Ltd., 0.972 g, 7.4 mol% with respect to the monomer) is dissolved in 70 g of cyclohexanone in order from the left It was dripped over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixture of 800 ml of hexane / 300 ml of ethyl acetate over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 13 g of polymer (1). The weight average molecular weight of the obtained polymer (1) was 8260 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.50.

  In the same manner as in Synthesis Example 2, polymers (2) to (40) and comparative polymers (1) to (2) were synthesized. Table 2 below shows the composition ratio (mol%, corresponding to each repeating unit in order from the left), weight average molecular weight, and degree of dispersion.

  The polymer structures described in Table 2 are shown below. The polymer structures 6-1 to 6-3 in Table 2 have the composition ratio (ratio of each repeating unit), weight average molecular weight, and dispersity shown in Table 2 in the polymer structure (6) shown below. Means a polymer. The same applies to the polymer structures 11-1 to 11-2.

Hereinafter, Examples 1-5, 11, 12, 18-20, 25, 34, 38, 39, 41, 43, 50, 59, 63, 64, 66 are referred to as Reference Examples 1-5, 11, 12, respectively. 18-20, 25, 34, 38, 39, 41, 43, 50, 59, 63, 64, 66.
[Examples 1 to 40 and Comparative Examples 1 and 2]
<Resist preparation>
The components shown in Table 3 below are dissolved in a solvent, and a solution having a solid content concentration of 5% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.1 μm, and an actinic ray-sensitive or radiation-sensitive resin. A composition was prepared. The prepared actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in Table 3. About each component in Table 3, the ratio at the time of using multiple is a mass ratio.
(Exposure conditions (1) ArF dry exposure)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied, and baked at 85 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. Using the obtained wafer ArF excimer laser scanner (manufactured by ASML, PAS 5500/1100, NA 0.75), the film was exposed through a 6% halftone mask with a 72 nm 1: 1 line and space pattern. Thereafter, heating was performed at 85 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

[DOF evaluation]
The depth of focus at which the line width of 72 nm ± 10% was reproduced at the optimum exposure dose was observed. A larger value is desirable because the tolerance for defocus is large.
[Development defect evaluation]
An actinic ray-sensitive or radiation-sensitive resin composition is uniformly applied on an 8-inch silicon substrate subjected to hexamethyldisilazane treatment by a spin coater, heated on a hot plate at 120 ° C. for 60 seconds, and dried. A resist film having a thickness of 0.10 μm was formed. This resist film was heated on a hot plate at 110 ° C. for 90 seconds without exposure. Further, the resist film was developed with an aqueous 2.38 wt% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried. The number of development defects of the sample wafer thus obtained was measured using a KLA2360 machine (manufactured by KLA Tencor). At this time, the number of defects in Comparative Example 1 was normalized to 1 and represented. A smaller numerical value corresponds to better development defect performance.

Hereinafter, abbreviations in the table are shown.
[Basic compounds]
DIA: 2,6-diisopropylaniline TBAH: tetrabutylammonium hydroxide TMEA: tris (methoxyethoxyethyl) amine PEA: N-phenyldiethanolamine DHA: N, N-dihexylaniline [surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-4: PF656 (manufactured by OMNOVA, fluorine-based)
W-5: PF6320 (manufactured by OMNOVA, fluorine-based)
〔solvent〕
A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: Cyclohexanone A3: γ-Butyrolactone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate

[Dissolution inhibitor compound]
D-1: t-butyl lithocholic acid

  From Table 3, it is clear that the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has improved DOF and development defects in ArF dry exposure.

[Examples 41 to 68 and Comparative Examples 3 to 4]
<Resist preparation>
The components shown in Table 4 below are dissolved in a solvent, and a solution having a solid content concentration of 5% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.1 μm, and an actinic ray-sensitive or radiation-sensitive resin. A composition was prepared. The prepared actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in Table 4. About each component in Table 4, the ratio at the time of using multiple is a mass ratio.
In Table 4, when the actinic ray-sensitive or radiation-sensitive resin composition contains a hydrophobic resin (HR), the addition form is indicated as “addition”. When the actinic ray-sensitive or radiation-sensitive resin composition does not contain a hydrophobic resin (HR), and after forming a resist film, a top coat protective film containing a hydrophobic resin (HR) is formed thereon. The addition form was labeled “TC”.
(Exposure condition (2) ArF immersion exposure)
An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied, and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. The obtained wafer was exposed through a 6% halftone mask of 65 nm 1: 1 line and space pattern using an ArF excimer laser immersion scanner (XT1250i, manufactured by ASML, NA 0.85). Ultra pure water was used as the immersion liquid. After heating at 130 ° C. for 60 seconds, developing with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, spin drying to form a resist pattern, and similarly DOF The development defects were evaluated.

When the addition form of the hydrophobic resin (HR) was “TC”, the following operation was performed after forming the resist film.
<Formation method of top coat>
On the resist film, a hydrophobic resin (HR) shown in Table 4 was dissolved in a solvent, applied by a spin coater, and the wafer was heated and dried at 115 ° C. for 60 seconds to form a top coat layer having a thickness of 0.05 μm. . At this time, the top coat application unevenness was observed, and it was confirmed that it was uniformly applied without application unevenness.
Abbreviations for solvents are as follows.
S-1; 2-ethylbutanol

  From Table 4, it is clear that the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has improved DOF and development defects in ArF immersion exposure.

Claims (12)

(A) It has two repeating units represented by the following general formula (A), has a repeating unit having a group represented by the following general formula (1 ′), and is soluble in an alkali developer by the action of an acid. An actinic ray-sensitive or radiation-sensitive resin composition containing a resin that increases the amount of acid and (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and having a total solid content in the composition of 1 to 10% by mass .

In general formula (A),
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 an alkyl group or a cycloalkyl group.
Two are bonded in rx ₁ to Rx _3, may form a cycloalkyl group.

In general formula (1 ′),
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; ₃ may combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group.
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.   The actinic ray-sensitive light according to claim 1, wherein the resin of component (A) further comprises a repeating unit containing a group having a lactone structure different from the group having a lactone structure represented by the general formula (1 '). Or radiation sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2 , wherein the resin of component (A) does not have an aromatic group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3 , wherein the resin of component (A) does not have a fluorine atom or a silicon atom. It further contains a hydrophobic resin (HR) having at least one of a fluorine atom and a silicon atom, and the content of the hydrophobic resin (HR) is 0.1 to 10 on the basis of the total solid content in the composition. The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-4 which is a mass%. The actinic-ray sensitive or radiation sensitive resin composition of Claim 5 in which the said hydrophobic resin (HR) contains the repeating unit represented by the following general formula (F4).

In general formula (F4),
R _{65 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{65 to} R ₆₈ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5 or 6 , wherein the hydrophobic resin (HR) further has at least one group selected from the following groups (x) to (z).
(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) a group decomposable by the action of an acid (A) It has two repeating units represented by the following general formula (A), has a repeating unit having a group represented by the following general formula (1), and has a solubility in an alkali developer due to the action of an acid. An actinic ray-sensitive or radiation-sensitive resin composition containing an increasing resin and (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, wherein the total solid concentration in the composition is 1 to 10% by mass.

In general formula (A),
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 an alkyl group or a cycloalkyl group.
Two are bonded in rx ₁ to Rx _3, may form a cycloalkyl group.

In general formula (1),
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; ₃ may combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y, when there are a plurality of them, each independently represents an electron-withdrawing group that is one of a cyano group, a nitro group, a carboxyl group , and an alkylsulfonyl group .
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8 , wherein the resin of component (A) has a repeating unit represented by the following general formula (2).

In general formula (2),
R ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom.
When there are a plurality of R _{2 s} , each independently represents a chain or cyclic alkylene group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; ₃ may combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently when there are two or more.
When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
k is the number of substituents and represents an integer of 0 to 8.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7. (A) Component resin has the repeating unit represented by following General formula (3), The actinic-ray sensitive or radiation sensitive resin composition of Claim 8 or 9 characterized by the above-mentioned.

In general formula (3),
R _1a represents a hydrogen atom or an alkyl group which may have a substituent.
R ₃ independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, when there are a plurality of R 3 s; ₃ may combine to form a ring.
X represents an alkylene group which may have a substituent, an oxygen atom or a sulfur atom.
k is the number of substituents and represents an integer of 0 to 8.
l represents the number of repetitions and represents an integer of 1 to 5.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 1 0, a pattern forming method film is formed, exposing the film, which comprises a step of developing . A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10 .