JP5124326B2 - Positive resist composition and pattern forming method - Google Patents

Description

  The present invention relates to a positive resist composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and also in a lithography process for other photo applications, and a pattern forming method using the same. It is. In particular, the present invention relates to a positive resist composition suitable for exposure with an immersion projection exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, and a pattern forming method using the same.

With the miniaturization of semiconductor elements, the exposure light source has become shorter in wavelength and the projection lens has a higher numerical aperture (high NA). ing. These can be expressed by the following equations as is generally well known.
(Resolving power) = k ₁ · (λ / NA)
(Depth of focus) = ± k ₂ · λ / NA ²
Where λ is the wavelength of the exposure light source, NA is the numerical aperture of the projection lens, and k ₁ and k ₂ are coefficients related to the process.

  An exposure machine using a F2 excimer laser having a wavelength of 157 nm as a light source has been studied for higher resolution by further shortening the wavelength. Because the materials to be used are very limited, it is very difficult to stabilize the manufacturing cost and quality of the equipment and materials, and it is possible that the exposure apparatus and resist having sufficient performance and stability will not be in time within the required period. Sex has come out.

As a technique for increasing the resolving power in an optical microscope, a so-called immersion method in which a high refractive index liquid (hereinafter also referred to as “immersion liquid”) is filled between a projection lens and a sample is known.
As for the "effect of immersion", the lambda ₀ is the wavelength of exposure light in air, the refractive index of the immersion liquid to air is n, the θ and convergence half of the light beam and when the NA ₀ = sin [theta, and immersion In this case, the above-described resolving power and depth of focus can be expressed by the following equations.
(Resolving power) = k ₁ · (λ ₀ / n) / NA ₀
(Depth of focus) = ± k ₂ · (λ ₀ / n) / NA ₀ ²
That is, the immersion effect is equivalent to using an exposure wavelength having a wavelength of 1 / n. In other words, in the case of a projection optical system with the same NA, the depth of focus can be increased n times by immersion.
This is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

An example of an apparatus in which this effect is applied to transfer of a fine image pattern of a semiconductor element is introduced in Patent Document 1 (Japanese Patent Laid-Open No. 57-153433) and the like.
Recent progress in immersion exposure technology is described in Non-Patent Document 1 (SPIE Proc 4688, 11 (2002)), Non-Patent Document 2 (J. Vac. Sci. Tecnol. B 17 (1999)), Non-Patent Document 3 (SPIE Proc 3999,2 (2000)). In the case of using an ArF excimer laser as a light source, pure water (refractive index of 1.44 at 193 nm) is considered to be most promising as an immersion liquid in terms of handling safety, transmittance at 193 nm, and refractive index. When an F2 excimer laser is used as a light source, a solution containing fluorine has been studied from the balance between transmittance and refractive index at 157 nm, but a sufficient product has not yet been found in terms of environmental safety and refractive index. It has not been. From the degree of immersion effect and the degree of completeness of the resist, the immersion exposure technique is considered to be installed in the ArF exposure machine earliest.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. Explaining by taking a positive chemical amplification image forming method as an example, the acid generator in the exposed area is decomposed by exposure to generate an acid upon exposure, and the generated acid is reacted as a reaction catalyst by post exposure baking (PEB). Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development. As a chemically amplified resist composition, for example, in Patent Document 2 (International Publication WO2005 / 003198 pamphlet) and Patent Document 3 (Japanese Patent Laid-Open No. 2002-303978), a resist in which two or more kinds of resins having a specific structure are mixed is used. Compositions are introduced. ArF excimer laser resists using a chemical amplification mechanism are now becoming mainstream, but there is a problem that the pattern collapses when exposed with a fine mask size, and improvement has been desired.

When a chemically amplified resist is applied to immersion exposure, the resist layer comes into contact with the immersion liquid at the time of exposure, so that the resist layer may be altered or components that have an adverse effect on the immersion liquid may exude from the resist layer. It has been pointed out. Patent Document 4 (International Publication WO 2004-068242 Pamphlet) describes an example in which resist performance changes by immersing a resist for ArF exposure in water before and after exposure, and points to a problem in immersion exposure. .
In the immersion exposure process, when exposure is performed using a scanning immersion exposure machine, if the immersion liquid does not move following the movement of the lens, the exposure speed is reduced, which affects the productivity. Concerned about giving. In the case where the immersion liquid is water, it is desired that the resist film is hydrophobic and has good water followability.

In addition, from the viewpoint of overall performance as a resist, it is extremely difficult to find an appropriate combination of resins, photoacid generators, additives, solvents, etc. used, and the line width is 100 nm or less. When forming a very fine pattern, even if the resolution performance is excellent, the formed line pattern collapses, resulting in a pattern collapse problem that causes defects during device manufacturing, and variations in the line pattern. There was a need for improved line edge roughness performance.
Here, the line edge roughness means that the resist line pattern and the edge of the substrate interface exhibit irregular shapes in a direction perpendicular to the line direction due to the characteristics of the resist. When this pattern is observed from directly above, the edges appear to be uneven (± several nm to several tens of nm). Since the unevenness is transferred to the substrate by an etching process, if the unevenness is large, an electrical characteristic defect is caused and the yield is lowered.

JP-A-57-153433 International Publication No. 05/003198 Pamphlet JP 2002-303978 A International Publication No. 04-068242 Pamphlet Proc. SPIE, 2002, Vol. 4688, p. 11 J.Vac.Sci.Tecnol.B 17 (1999) Proc. SPIE, 2000, Vol. 3999, p. 2

  In view of the above-mentioned problems of the prior art, the object of the present invention is to improve the line edge roughness due to normal exposure and immersion exposure, and to provide a positive resist composition excellent in water followability in immersion exposure and It is to provide a pattern forming method using the same.

一般式（Ｉ）中、
Ｘａ _１ は、水素原子、アルキル基、シアノ基又はハロゲン原子を表す。
Ｒｙ _１ 〜Ｒｙ _３ は、各々独立に、アルキル基又はシクロアルキル基を表す。Ｒｙ _１ 〜Ｒｙ _３ の内の少なくとも２つが結合して環構造を形成してもよい。
Ｚは、２価の連結基を表す。

式（Ｃ−Ｉ）〜（Ｃ−ＩＩＩ）中、
Ｒ _１ は、各々独立に水素原子またはメチル基を表す。
Ｒ _２ は、各々独立に１つ以上の−ＣＨ _３ 部分構造を有する炭化水素基を表す。
Ｐ _１ は、単結合、またはアルキレン、エーテル、またはそれらを２つ以上有する連結基を表す。
Ｐ _２ は、−Ｏ−、−ＮＲ−（Ｒは水素原子またはアルキル）、−ＮＨＳＯ _２ −から選ばれる連結基を表す。
ｎは１〜４の整数を表す。
〔２〕
一般式（Ｉ）におけるＺが、２価の鎖状炭化水素基又は２価の環状炭化水素基であることを特徴とする請求項１に記載のポジ型レジスト組成物。
〔３〕
一般式（Ｉ）におけるＺが、２価の鎖状炭化水素基であることを特徴とする〔１〕又は〔２〕に記載のポジ型レジスト組成物。
〔４〕
（Ａ）成分の樹脂が、更に、ラクトン基、水酸基、シアノ基及び酸基から選ばれる少なくとも１種類を有する繰り返し単位を有することを特徴とする〔１〕〜〔３〕のいずれかに記載のポジ型レジスト組成物。
〔５〕
（Ｂ）成分として、下記一般式（ＢＩＩ）で表される酸を発生する化合物を含有することを特徴とする〔１〕〜〔４〕のいずれかに記載のポジ型レジスト組成物。

一般式（ＢＩＩ）中、
Ｒｂ _１ は、電子吸引性基を有する基を表す。
Ｒｂ _２ は、電子吸引性基を有さない有機基を表す。
ｍ、ｎは各々０〜５の整数を表す。但しｍ＋ｎ≦５である。
ｍが２以上の場合、複数存在するＲｂ _１ は同一でも異なっていてもよい。
ｎが２以上の場合、複数存在するＲｂ _２ は同一でも異なっていてもよい。
〔６〕
一般式（ＢＩＩ）において、ｍが１〜５であって、Ｒｂ _１ の電子吸引性基がフッ素原子、フロロアルキル基、ニトロ基、エステル基、シアノ基から選ばれる少なくとも１種であることを特徴とする〔５〕に記載のポジ型レジスト組成物。
〔７〕
（Ｃ）成分の樹脂が、さらに、下記一般式（Ｃ）で表される繰り返し単位を含有することを特徴とする、〔１〕〜〔６〕のいずれかに記載のポジ型レジスト組成物。

一般式（Ｃ）に於いて、
Ｘ _１ 、Ｘ _２ 及びＸ _３ は、各々独立に、水素原子、アルキル基又はハロゲン原子を表す。
Ｌは、単結合又は２価の連結基を表す。
Ｒｐ _１ は、酸分解性基を表す。
〔８〕
一般式（Ｃ）で表される繰り返し単位が、下記一般式（Ｃ１）で表される繰り返し単位であることを特徴とする、〔７〕に記載のポジ型レジスト組成物。

一般式（Ｃ１）に於いて、
Ｘ _１ 、Ｘ _２ 及びＸ _３ は、各々独立に、水素原子、アルキル基又はハロゲン原子を表す。
Ｒ _１２ 、Ｒ _１３ 及びＲ _１４ は、各々独立に、アルキル基、シクロアルキル基、アルケニル基又はアリール基を表す。但し、Ｒ _１２ 、Ｒ _１３ 及びＲ _１４ の内の少なくとも１つは、アルキル基を表す。Ｒ _１２ 、Ｒ _１３ 及びＲ _１４ の内の２つが、結合して環を形成してもよい。
〔９〕
一般式（Ｃ−Ｉ）〜（Ｃ−ＩＩＩ）において、Ｒ _２ が、−ＣＨ _３ 部分構造を２つ以上有することを特徴とする〔１〕〜〔８〕のいずれかに記載のポジ型レジスト組成物。
〔１０〕
（Ｃ）成分が、（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、及び（ｚ）酸の作用により分解する基から選ばれる基を少なくとも一つ有することを特徴とする〔１〕〜〔９〕のいずれかに記載のポジ型レジスト組成物。
〔１１〕
一般式（Ｃ−Ｉ）〜（Ｃ−ＩＩＩ）から選ばれる繰り返し単位の少なくとも１つの総含有量が、（Ｃ）成分の樹脂中の全繰り返し単位に対し、８０〜１００ｍｏｌ％であることを特徴とする〔１〕〜〔１０〕のいずれかに記載のポジ型レジスト組成物。
〔１２〕
（Ｃ）成分の樹脂の含有量が、ポジ型レジスト組成物の固形分を基準にして０．１〜１０質量％であることを特徴とする〔１〕〜〔１１〕のいずれかに記載のポジ型レジスト組成物。
〔１３〕
波長が２００ｎｍ以下の露光に用いることを特徴とする〔１〕〜〔１２〕のいずれかに記載のポジ型レジスト組成物。
〔１４〕
〔１〕〜〔１３〕のいずれかに記載のポジ型レジスト組成物により形成されるレジスト膜。
〔１５〕
〔１４〕に記載のレジスト膜を露光、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。
〔１６〕
液浸液を介してレジスト膜に露光することを特徴とする〔１５〕に記載のパターン形成方法。
本発明は上記の〔１〕〜〔１６〕に関するものであるが、その他の事項についても記載した。
＜１＞（Ａ）下記一般式（Ｉ）で表される酸分解性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速度が増大する樹脂、（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、（Ｃ）フッ素および珪素を含有せず、下記一般式（Ｃ−Ｉ）〜（Ｃ−ＩＩＩ）から選ばれる繰り返し単位を少なくとも１つ有する樹脂、および（Ｄ）溶剤、を含有することを特徴とするポジ型感光性組成物。

一般式（Ｉ）中、
Ｘａ_１は、水素原子、アルキル基、シアノ基又はハロゲン原子を表す。
Ｒｙ_１〜Ｒｙ_３は、各々独立に、アルキル基又はシクロアルキル基を表す。Ｒｙ_１〜Ｒｙ_３の内の少なくとも２つが結合して環構造を形成してもよい。
Ｚは、２価の連結基を表す。

式（Ｃ−Ｉ）〜（Ｃ−ＩＩＩ）中、
Ｒ_１は、各々独立に水素原子またはメチル基を表す。
Ｒ_２は、各々独立に２つ以上の−ＣＨ_３部分構造を有する炭化水素基を表す。
Ｐ_１は、単結合、またはアルキレン、エーテル、またはそれらを２つ以上有する連結基を表す。
Ｐ_２は、−Ｏ−、−ＮＲ−（Ｒは水素原子またはアルキル）、−ＮＨＳＯ_２−から選ばれる連結基を表す。
ｎは１〜４の整数を表す。 [1]
(A) a resin having an acid-decomposable repeating unit represented by the following general formula (I), which increases the dissolution rate in an alkali developer by the action of an acid; (B) an acid by irradiation with actinic rays or radiation; A generated compound, (C) a resin that does not contain fluorine and silicon and has at least one repeating unit selected from the following general formulas (CI) to (C-III), and (D) a solvent A positive photosensitive composition, wherein the content of the resin of component (C) is 0.1 to 20% by mass based on the solid content of the positive resist composition.

In general formula (I),
Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
Ry ₁ to Ry ₃ each independently represents an alkyl group or a cycloalkyl group. At least two members out of Ry _{1 to} Ry ₃ may be bonded to form a ring structure.
Z represents a divalent linking group.

In formulas (CI) to (C-III),
R ₁ each independently represents a hydrogen atom or a methyl group.
R ₂ each independently represents a hydrocarbon group having one or more —CH ₃ partial structures.
P ₁ represents a single bond or alkylene, ether, or a linking group having two or more thereof.
P ₂ represents a linking group selected from —O—, —NR— (R is a hydrogen atom or alkyl), and —NHSO ₂ —.
n represents an integer of 1 to 4.
[2]
The positive resist composition according to claim 1, wherein Z in the general formula (I) is a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group.
[3]
The positive resist composition as described in [1] or [2], wherein Z in the general formula (I) is a divalent chain hydrocarbon group.
[4]
The resin as component (A) further has a repeating unit having at least one kind selected from a lactone group, a hydroxyl group, a cyano group, and an acid group, according to any one of [1] to [3] Positive resist composition.
[5]
(B) The positive resist composition as described in any one of [1] to [4], which contains a compound capable of generating an acid represented by the following general formula (BII) as a component.

In general formula (BII),
Rb ₁ represents a group having an electron-withdrawing group.
Rb ₂ represents an organic group having no electron withdrawing group.
m and n each represents an integer of 0 to 5. However, m + n ≦ 5.
When m is 2 or more, a plurality of Rb ₁ may be the same or different.
When n is 2 or more, a plurality of Rb ₂ may be the same or different.
[6]
In general formula (BII), m is 1 to 5, and the electron-withdrawing group of Rb ₁ is at least one selected from a fluorine atom, a fluoroalkyl group, a nitro group, an ester group, and a cyano group. The positive resist composition as described in [5].
[7]
The positive resist composition as described in any one of [1] to [6], wherein the resin as the component (C) further contains a repeating unit represented by the following general formula (C).

In general formula (C),
X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom, an alkyl group or a halogen atom.
L represents a single bond or a divalent linking group.
Rp ₁ represents an acid-decomposable group.
[8]
The positive resist composition as described in [7], wherein the repeating unit represented by the general formula (C) is a repeating unit represented by the following general formula (C1).

In general formula (C1),
X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom, an alkyl group or a halogen atom.
R ₁₂ , R ₁₃ and R ₁₄ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. However, at least one of R ₁₂ , R ₁₃ and R ₁₄ represents an alkyl group. Two of R ₁₂ , R ₁₃ and R ₁₄ may combine to form a ring.
[9]
The positive resist according to any one of [1] to [8], wherein in general formulas (CI) to (C-III), R ₂ has two or more —CH ₃ partial structures. Composition.
[10]
Component (C) is selected from (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, and (z) a group that decomposes by the action of an acid. The positive resist composition as described in any one of [1] to [9], wherein the positive resist composition has at least one group.
[11]
The total content of at least one repeating unit selected from the general formulas (CI) to (C-III) is 80 to 100 mol% with respect to all repeating units in the resin of the component (C). The positive resist composition according to any one of [1] to [10].
[12]
The content of the resin as the component (C) is 0.1 to 10% by mass based on the solid content of the positive resist composition, according to any one of [1] to [11] Positive resist composition.
[13]
The positive resist composition as described in any one of [1] to [12], which is used for exposure having a wavelength of 200 nm or less.
[14]
[1] A resist film formed from the positive resist composition according to any one of [13].
[15]
[14] A pattern forming method comprising a step of exposing and developing the resist film according to [14].
[16]
The pattern forming method according to [15], wherein the resist film is exposed through an immersion liquid.
The present invention relates to the above [1] to [16], but other matters are also described.
<1> (A) a resin having an acid-decomposable repeating unit represented by the following general formula (I), which increases the dissolution rate in an alkali developer by the action of an acid, (B) by irradiation with actinic rays or radiation A compound that generates an acid, (C) a resin that does not contain fluorine and silicon and has at least one repeating unit selected from the following general formulas (CI) to (C-III), and (D) a solvent, A positive photosensitive composition comprising:

In general formula (I),
Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
Ry _{1 to} Ry ₃ each independently represents an alkyl group or a cycloalkyl group. At least two members out of Ry _{1 to} Ry ₃ may be bonded to form a ring structure.
Z represents a divalent linking group.

In formulas (CI) to (C-III),
R ₁ each independently represents a hydrogen atom or a methyl group.
R ₂ independently represents a hydrocarbon group having two or more —CH ₃ partial structures.
P ₁ represents a single bond or alkylene, ether, or a linking group having two or more thereof.
P ₂ represents a linking group selected from —O—, —NR— (R is a hydrogen atom or alkyl), and —NHSO ₂ —.
n represents an integer of 1 to 4 .

<2>
The positive resist composition as described in <1> above, wherein Z in the general formula (I) is a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group.

<3>
The positive resin as described in <1> or <2> above, wherein the resin as the component (A) further has a repeating unit having at least one kind selected from a lactone group, a hydroxyl group, a cyano group, and an acid group. Resist composition.

一般式（ＢＩＩ）中、
Ｒｂ₁は、電子吸引性基を有する基を表す。
Ｒｂ₂は、電子吸引性基を有さない有機基を表す。
ｍ、ｎは各々０〜５の整数を表す。但しｍ＋ｎ≦５である。
ｍが２以上の場合、複数存在するＲｂ₁は同一でも異なっていてもよい。
ｎが２以上の場合、複数存在するＲｂ₂は同一でも異なっていてもよい。 <4> The positive resist composition as described in any one of <1> to <3> above, which contains a compound capable of generating an acid represented by the following general formula (BII) as the component (B) object.

In general formula (BII),
Rb ₁ represents a group having an electron-withdrawing group.
Rb ₂ represents an organic group having no electron-withdrawing group.
m and n each represents an integer of 0 to 5. However, m + n ≦ 5.
When m is 2 or more, a plurality of Rb ₁ may be the same or different.
When n is 2 or more, a plurality of Rb ₂ may be the same or different.

<5>
In the general formula (BII), m is 1 to 5, and the electron withdrawing group of Rb ₁ is at least one selected from a fluorine atom, a fluoroalkyl group, a nitro group, an ester group, and a cyano group. The positive resist composition as described in <4> above.

一般式（Ｃ）に於いて、
Ｘ₁、Ｘ₂及びＸ₃は、各々独立に、水素原子、アルキル基又はハロゲン原子を表す。
Ｌは、単結合又は２価の連結基を表す。
Ｒｐ₁は、酸分解性基を表す。 <6> The positive type resin according to any one of <1> to <5> above, wherein the resin as the component (C) further contains a repeating unit represented by the following general formula (C): Resist composition.

In general formula (C),
X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom, an alkyl group or a halogen atom.
L represents a single bond or a divalent linking group.
Rp ₁ represents an acid-decomposable group.

一般式（Ｃ１）に於いて、
Ｘ₁、Ｘ₂及びＸ₃は、各々独立に、水素原子、アルキル基又はハロゲン原子を表す。
Ｒ₁₂、Ｒ₁₃及びＲ₁₄は、各々独立に、アルキル基、シクロアルキル基、アルケニル基又はアリール基を表す。但し、Ｒ₁₂、Ｒ₁₃及びＲ₁₄の内の少なくとも１つは、アルキル基を表す。Ｒ₁₂、Ｒ₁₃及びＲ₁₄の内の２つが、結合して環を形成してもよい。 <7>
The positive resist composition as described in <6> above, wherein the repeating unit represented by the general formula (C) is a repeating unit represented by the following general formula (C1).

In general formula (C1),
X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom, an alkyl group or a halogen atom.
R ₁₂ , R ₁₃ and R ₁₄ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. However, at least one of R ₁₂ , R ₁₃ and R ₁₄ represents an alkyl group. Two of R ₁₂ , R ₁₃ and R ₁₄ may combine to form a ring.

<8>
The positive resist composition as described in any one of <1> to <7> above, which is used for exposure having a wavelength of 200 nm or less.

<9>
The positive resist composition as described in <4> or <5> above, wherein in the general formula (BII), the organic group having no electron withdrawing group of Rb ₂ is a group having an alicyclic group object.

<10>
Furthermore, basic compound (E) is contained, The positive resist composition in any one of said <1>-<9> characterized by the above-mentioned.

<11>
The positive resist composition as described in <10> above, which contains at least one of 2,6-diisopropylaniline and tetrabutylammonium hydroxide as the basic compound (E).

<12>
The positive resist composition according to any one of <1> to <11> above, which contains at least one of propylene glycol monomethyl ether acetate, 2-heptanone, and γ-butyrolactone as the solvent (D).

<13>
Furthermore, surfactant (F) is contained, The positive resist composition in any one of said <1>-<12> characterized by the above-mentioned.

<14>
A pattern forming method comprising: forming a resist film from the positive resist composition as described in any one of <1> to <13> above, and exposing and developing the resist film.

<15>
The pattern forming method as described in <14> above, wherein the resist film is exposed through an immersion liquid.

  The present invention provides a positive resist composition having improved line edge roughness due to normal exposure and immersion exposure, and excellent in water followability during immersion exposure, and a pattern forming method using the same.

Hereinafter, the present invention will be described in detail.
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) Resin whose dissolution rate in an alkaline developer is increased by the action of an acid The resin whose dissolution rate in an alkaline developer is increased by the action of an acid used in the positive photosensitive composition of the present invention is as follows. A resin having an acid-decomposable repeating unit represented by formula (I) (also referred to as “resin of component (A)”).

In general formula (I),
Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
Ry _{1 to} Ry ₃ each independently represents an alkyl group or a cycloalkyl group. At least two members out of Ry _{1 to} Ry ₃ may be bonded to form a monocyclic or polycyclic hydrocarbon structure.
Z represents a divalent linking group.

In general formula (I), the alkyl group of Xa ₁ may be substituted with a hydroxyl group, a halogen atom, or the like.
Xa ₁ is preferably a hydrogen atom or a methyl group.
The alkyl group of Ry _{1 to} Ry ₃ may be either a linear alkyl group or a branched alkyl group, and may have a substituent. Examples of the substituent that may be included include a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, and a cyano group. Preferred linear and branched alkyl groups have 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups. And preferably a methyl group or an ethyl group.
The cycloalkyl group of Ry ₁ to Ry _3, for example, a monocyclic cycloalkyl group having 3 to 8 carbon atoms may be a cycloalkyl group polycyclic 7-14 carbon atoms, optionally substituted Also good. Preferred examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclopropyl group. Preferred examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornane group, a tetracyclododecanyl group, a tricyclodecanyl group, and a diamantyl group.

As the monocyclic hydrocarbon structure formed by combining at least two members out of Ry _{1 to} Ry ₃ , a cyclopentyl group and a cyclohexyl group are preferable. As the polycyclic hydrocarbon structure formed by bonding at least two of Ry _{1 to} Ry ₃ , an adamantyl group, a norbornyl group, and a tetracyclododecanyl group are preferable.
Z is preferably a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group. Moreover, it may have a substituent, and examples of the substituent that may have a fluorine atom, chlorine atom, bromine atom, hydroxyl group, and cyano group. Z is preferably a divalent linking group having 1 to 20 carbon atoms, more preferably a chain alkylene group having 1 to 4 carbon atoms, a cyclic alkylene group having 5 to 20 carbon atoms, or a combination thereof. It is. Examples of the chain alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group, which may be linear or branched. A methylene group is preferred. Examples of the cyclic alkylene group having 5 to 20 carbon atoms include monocyclic cyclic alkylene groups such as cyclopentylene group and cyclohexylene group, and polycyclic cyclic alkylene groups such as norbornylene group and adamantylene group. An adamantylene group is preferred.

  The polymerizable compound for forming the repeating unit represented by the general formula (I) can be easily synthesized by a known method. For example, using a method similar to the method described in JP-A-2005-331918, as shown in the following formula, an alcohol and a carboxylic acid halide compound are reacted under basic conditions, and then this and a carboxylic acid compound are converted into a base. It can be synthesized by reacting under sexual conditions.

  Preferred specific examples of the repeating unit represented by formula (I) are shown below, but the present invention is not limited thereto.

  The repeating unit represented by the general formula (I) is decomposed by the action of an acid to generate a carboxyl group, and the dissolution rate in an alkaline developer increases.

In addition to the acid-decomposable repeating unit represented by formula (I), the resin of component (A) may further have another acid-decomposable repeating unit.
Other acid-decomposable repeating units other than the acid-decomposable repeating unit represented by the general formula (I) are preferably repeating units represented by the following general formula (II).

In general formula (II),
Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and is the same as Xa ₁ in the general formula (I).
Rx _{1 to} Rx ₃ each independently represents an alkyl group or a cycloalkyl group. At least two of Rx _{1 to} Rx ₃ may be bonded to form a cycloalkyl group.

The alkyl group of Rx _{1 to} Rx ₃ is linear or branched having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. The shape is preferred.
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.
The cycloalkyl group formed by bonding at least two of Rx _{1 to} Rx ₃ includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. And a polycyclic cycloalkyl group such as an adamantyl group is preferred.
These groups of Rx _{1 to} Rx ₃ may further have a substituent, and examples of the substituent that may be included include a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, and a cyano group. Can be mentioned.
It is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to each other to bond the above monocyclic or polycyclic cycloalkyl group.

  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.

  Preferred repeating units represented by the general formula (II) are 1, 2, 10, 11, 12, 13, and 14 repeating units in the above specific examples.

  When the repeating unit having an acid-decomposable group represented by the general formula (I) and a repeating unit having another acid-decomposable group (preferably a repeating unit represented by the general formula (II)) are used in combination, The ratio of the repeating unit having an acid-decomposable group represented by the general formula (I) and the repeating unit having another acid-decomposable group is 90:10 to 10:90, more preferably 80 in terms of molar ratio. : 20 to 20:80.

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

  The resin of component (A) preferably further has a repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group.

The resin of component (A) preferably has a repeating unit having a lactone structure.
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 (LC1-16). 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), (LC1-14), and a specific lactone structure is used. This improves line edge roughness and development defects.

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 1 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. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of 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 (LC1-16) 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 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, branched alkylene group, 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 (LC1-16).

  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 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 lactone structure are given below, but the present invention is not limited thereto.

  Particularly preferred repeating units having a lactone structure include the following repeating units. By selecting the optimum lactone structure, the pattern profile and the density dependence become good.

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), it is more preferable that _two members out 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 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-attracting 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, 1-20 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.

  As the repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group, more preferably, a repeating unit having at least two groups selected from a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group Preferably, it is a repeating unit having a cyano group and a lactone group. Particularly preferred is a repeating unit having a structure in which a cyano group is substituted on the lactone structure of LCI-4.

  The resin as the component (A) may further contain 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, cyclohexyl (meth) acrylate, and the like.

  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.

  As a result, the performance required for the resin of component (A), in particular, (1) solubility in coating solvent, (2) film forming property (glass transition point), (3) alkali developability, (4) film slipping Fine adjustments such as (hydrophobicity and alkali-soluble group selection), (5) adhesion of the unexposed part to the substrate, and (6) dry etching resistance are possible.

  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 positive photosensitive 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.

  As the resin of component (A), preferably, all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units. More preferably, the (meth) acrylate repeating unit having an acid-decomposable group represented by the general formula (I) is 20 to 50 mol%, the (meth) acrylate repeating unit having a lactone structure is 20 to 50 mol%, It is a copolymer having 5 to 30 mol% of (meth) acrylate-based repeating units having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and further containing 0 to 20 mol% of other (meth) acrylate-based repeating units. .

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 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 positive photosensitive composition of the present invention. Thereby, the generation of particles during storage 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 is 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 from 1,000 to 200,000, more preferably from 3,000 to 20,000, and most preferably from 5,000 to 200 in terms of polystyrene by GPC method. 15,000. 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 from 1 to 5, preferably from 1 to 3, more preferably from 1 to 2. 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.

When the resin of component (A) is used in a positive photosensitive composition that irradiates KrF excimer laser light, electron beam, X-ray, high energy light (EUV, etc.) having a wavelength of 50 nm or less, The resin preferably has a repeating unit of the general formula (I) and further a repeating unit having a hydroxystyrene structure. Examples of the repeating unit having a hydroxystyrene structure include o-, m-, p-hydroxystyrene and / or hydroxystyrene protected with an acid-decomposable group. The hydroxystyrene repeating unit protected with an acid-decomposable group is preferably 1-alkoxyethoxystyrene or t-butylcarbonyloxystyrene.
In addition to the repeating unit represented by the general formula (I) and the repeating unit having a hydroxystyrene structure, it may further have a repeating unit represented by the general formula (II).

Specific examples of the resin having a repeating unit having a hydroxystyrene structure and a repeating unit represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto. In specific examples, Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.

In the positive photosensitive composition of the present invention, the blending amount of the component (A) resin in the entire composition is preferably 50 to 99.99% by mass, more preferably 60 to 99.0% by mass in the total solid content. %.
In the present invention, the resin of component (A) may be used alone or in combination.

(B) Compound that generates an acid upon irradiation with actinic rays or radiation The positive photosensitive composition of the present invention is a compound that generates an acid upon irradiation with an actinic ray or radiation (“acid generator” and “(B) component”. Also referred to as “compounds of”.

  As a compound which decomposes | disassembles by irradiation of actinic light or a radiation and generates an acid, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imide sulfonate, oxime sulfonate, o-nitrobenzyl sulfonate can be mentioned, for example.

  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.

The acid generator preferably has a non-nucleophilic anion, preferably a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF. _6- ^{and the} like, and an organic anion containing a carbon atom is preferable.

  Examples of the non-nucleophilic anion include organic anions represented by the following formulas AN1 to AN4.

Rc ₁ represents an organic group.
Raised those having 1 to 30 carbon atoms as an organic group in rc ₁ preferably substituted alkyl which may have or substituted with optionally be aryl group or the plurality is a single bond, -O -, - _{CO 2 -, - S -,} - SO 3 -, - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.
Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with the bonded alkyl group or aryl group.

The organic group of Rc ₁ is more preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. When Rc1 has 5 or more carbon atoms, at least one carbon atom is preferably substituted with a hydrogen atom, and more preferably, the number of hydrogen atoms is larger than that of fluorine atoms. By not having a perfluoroalkyl group having 5 or more carbon atoms, ecotoxicity is reduced.
Rc ₁ is also preferably a group represented by the following general formula.

Rc ₆ represents a perfluoroalkylene group, 3-5 fluorine atoms and / or 1-3 phenylene group substituted with a fluoroalkyl group.
Ax represents a linking group (preferably a single _{bond, -O -, - CO 2 -} , - S -, - SO 3 -, - SO 2 N (Rd1) -. Rd 1 represents a hydrogen atom, an alkyl group, Rc ₇ And may form a ring structure.

Rc ₇ represents a hydrogen atom, a fluorine atom, an optionally substituted straight chain, branched, monocyclic or polycyclic alkyl group, an aryl group which may be substituted. The optionally substituted alkyl group and aryl group preferably do not contain a fluorine atom as a substituent.
Rc ₃ , Rc ₄ and Rc ₅ represent an organic group.
Preferred examples of the organic group for Rc ₃ , Rc ₄ and Rc ₅ include the same organic groups as those for Rc ₁ .
Rc ₃ and Rc ₄ may combine to form a ring. Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred. Rc ₃ and Rc ₄ are preferably bonded to form a ring, so that the acidity of the acid generated by light irradiation is increased and the sensitivity is improved, which is preferable.

  As the acid generator used in the present invention, a compound capable of generating an acid represented by formula (BII) is preferable.

In general formula (BII),
Rb ₁ represents a group having an electron-withdrawing group.
Rb ₂ represents an organic group having no electron-withdrawing group.
m and n each represents an integer of 0 to 5. However, m + n ≦ 5.
When m is 2 or more, a plurality of Rb ₁ may be the same or different.
When n is 2 or more, a plurality of Rb ₂ may be the same or different.

  m is preferably an integer of 1 to 5, more preferably an integer of 2 to 5. By having an electron-withdrawing group, the acidity of the acid generated upon irradiation with actinic rays increases, and the sensitivity is improved.

The group having an electron-withdrawing group as Rb ₁ is a group having at least one electron-withdrawing group, and preferably has 10 or less carbon atoms. The group having an electron withdrawing group may be the electron withdrawing group itself.
As the electron withdrawing group, a fluorine atom, a fluoroalkyl group, a nitro group, an ester group and a cyano group are preferable, and a fluorine atom is more preferable.

Preferably an organic group having 1 to 20 carbon atoms as an organic group having no electron withdrawing group in rb _2, more preferably 4 to 20 carbon atoms, more preferably from 4 to 15 carbon atoms. Preferred organic groups include alkyl groups, alkoxy groups, alkylthio groups, acyl groups, acyloxy groups, acylamino groups, alkylsulfonyloxy groups, alkylsulfonylamino groups, and the like. These alkyl chains may have a linking group having a hetero atom. Preferred examples of the linking group having a hetero atom include —C (═O) O—, —C (═O) —, —SO ₂ —, —SO ₃ —, —SO ₂ N (A2) —, —O—, -S-, etc. are mentioned, and two or more of these may be combined. Here, A2 represents a hydrogen atom or an optionally substituted alkyl group. When two or more are combined, it is preferably via a linking group having no hetero atom such as an alkylene group or an arylene group.
These groups may have a further substituent, and preferred examples of the further substituent include a hydroxyl group, a carboxyl group, a sulfo group, and a formyl group.

In general formula (II), m is an integer of 1 to 5, n is an integer of 1 to 5, m + n ≦ 5, and Rb ₁ or Rb ₂ preferably contains an alkyl structure having 4 to 20 carbon atoms. By containing an alkyl structure having 4 to 20 carbon atoms, the diffusibility of the acid generated by irradiation with actinic rays is suppressed, and the exposure latitude is improved.

In the general formula (II), Rb ₁ and Rb ₂ preferably have an alicyclic group.
In particular, the organic group having no electron-withdrawing group of Rb ₂ is preferably a group having an alicyclic group.

  Specific examples of the acid represented by the general formula (II) are shown below.

  Examples of the compound that generates an acid represented by the general formula (BII) upon irradiation with actinic rays or radiation include, for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imidosulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate. Can be mentioned.

  Among the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by the following general formulas (ZIa) and (ZIIa) can be exemplified.

In the above general formula (ZIa), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
Xd- represents an anion of an acid represented by the general formula (BII).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (ZI-1a), (ZI-2a) and (ZI-3a) described later.

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

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

Compound (ZI-1a) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZIa), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
Arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group with the remaining being an alkyl group.
Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, and an aryldialkylsulfonium compound.
The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. 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 that the arylsulfonium compound has as necessary is preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec. -Butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like can be mentioned.
The aryl group and alkyl group of R _{201 to} R ₂₀₃ are an alkyl group (eg, having 1 to 15 carbon atoms), an aryl group (eg, having 6 to 14 carbon atoms), an alkoxy group (eg, having 1 to 15 carbon atoms), a halogen atom, You may have a hydroxyl group and a phenylthio group as a substituent. Preferred substituents are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, most preferably alkyl groups having 1 to 4 carbon atoms, It is a C1-C4 alkoxy group. 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.
The arylsulfonium cation is preferably an optionally substituted triphenylsulfonium cation, an optionally substituted naphthyltetrahydrothiophenium cation, and an optionally substituted phenyltetrahydrothiophenium cation.

Next, the compound (ZI-2a) will be described.
Compound (ZI-2a) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZIa) each independently represents an organic group containing 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 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group, more preferably a linear, branched, or cyclic 2-oxoalkyl group, An alkoxycarbonylmethyl group, most preferably a linear, branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, branched, or cyclic, preferably a linear or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group) and cyclic alkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be linear, branched or cyclic, and preferably includes a group having> C═O at the 2-position of the above alkyl group. it can.
The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R _203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 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.
Two members out of R _{201 to} R ₂₀₃ may combine 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).

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

R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.
R _6c and R _7c represent a hydrogen atom or an alkyl group.
Rx and Ry each independently represents an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group.
Any two or more of R _{1c to} R _5c , 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, a sulfur atom, an ester bond, and an amide bond. May be included.
Xd ⁻ represents an anion of an acid represented by the general formula (BII).

The alkyl group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms. Group (for example, methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group), C3-C8 cyclic alkyl group (for example, cyclopentyl group, cyclohexyl group) ).
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 either a straight chain of R _1c to R _5c, branched, cyclic alkyl group, or a linear, branched or cyclic alkoxy group, more preferably the sum of the carbon atoms of R _5c from R _1c 2 to 15 It is. 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 as R _x and R _y include the same alkyl groups as R _{1c to} R _5c .
Examples of the 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group as R _{1c to} R _5c .
Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _{1c to} R _5c .
Examples of the group formed by combining R _x and R _y include a butylene group and a pentylene group.

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

In the general formula (ZIIa), R ₂₀₄ ~R ₂₀₅ each independently represents an alkyl group which may have an optionally substituted aryl group or a substituent.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _205, more preferably a phenyl group.
The alkyl group as R ₂₀₄ to R ₂₀₅ may be linear, branched, or cyclic, preferably a linear or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group) and cyclic alkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
The R ₂₀₄ to R ₂₀₅ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), an aryl group (e.g. having 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms ), Halogen atoms, hydroxyl groups, phenylthio groups, and the like.

  Of the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by the following general formulas (ZIIIa) and (ZIVa) can be further exemplified.

In general formulas (ZIIIa) and (ZIVa),
Xd represents a monovalent group obtained by removing a hydrogen atom from the acid represented by formula (BII).
_R207 and _{R208 each} represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or an electron-withdrawing group. R ₂₀₇ is preferably a substituted or unsubstituted aryl group.
R ₂₀₈ is preferably an electron-withdrawing group, more preferably a cyano group or a fluoroalkyl group.
A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group.

  Of the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, more preferred are compounds represented by the general formulas (ZIa) to (ZIIIa), and even more preferred are compounds represented by (ZIa). And most preferably the compounds represented by (ZI-1a) to (ZI-3a).

  Among the (B) components, examples of particularly preferable ones are listed below, but are not limited thereto.

  Other preferable acid generators include, for example, the following, but are not limited thereto.

  (B) The compound of a component can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.

  The content of the component (B) compound in the composition is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, still more preferably 3 to 8%, based on the total solid content of the resist composition. % By mass, particularly preferably 4 to 7% by mass.

(C) Resin which does not contain fluorine and silicon and has a repeating unit selected from the following general formulas (CI) to (C-III) The photosensitive composition of the present invention does not contain fluorine and silicon, A resin (C) having a repeating unit selected from the following general formulas (CI) to (C-III) (hereinafter also referred to as a hydrophobic resin (HR)) is contained.

In the formulas (CI) to (C-III),
R ₁ each independently represents a hydrogen atom or a methyl group.
Each R ₂ independently represents a hydrocarbon group having one or more —CH ₃ partial structures (ie, methyl groups).
P ₁ represents a single bond or alkylene, ether, or a linking group having two or more thereof.
P ₂ represents a linking group selected from —O—, —NR— (R is a hydrogen atom or alkyl), and —NHSO ₂ —.
n represents an integer of 1 to 4.
These repeating units may be one or a plurality of repeating units may be combined.

In the formulas (CI) to (C-III), the hydrocarbon group having one or more —CH ₃ partial structures (that is, methyl groups) of R ₂ is alkyl having one or more —CH ₃ partial structures. group, A alkyl substituted cycloalkyl group, an alkenyl group, an alkyl-substituted alkenyl group, an alkyl-substituted cycloalkenyl group, an alkyl-substituted aryl groups include alkyl-substituted aralkyl group, an alkyl group, an alkyl-substituted cycloalkyl group. Hydrocarbon group having one or more -CH ₃ partial structure R ₂ more preferably has a -CH ₃ partial structures of two or more.

The alkyl group having at least one —CH ₃ partial structure in R ₂ is preferably a branched alkyl group having 3 to 20 carbon atoms. Specific examples of preferable alkyl groups include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5- Examples thereof include a dimethyl-3-heptyl group and 2,3,5,7-tetramethyl-4-heptyl group. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group is there.
The alkyl group having one —CH ₃ partial structure in R ₂ is preferably a linear alkyl group having 1 to 20 carbon atoms. Specific examples of preferred alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl groups.

The cycloalkyl group in R ₂ may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25.
Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and tricyclodecanyl group. More preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.
The alkenyl group in R ₂ is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, and more preferably a branched alkenyl group.
The aryl group in R ₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The aralkyl group in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Specific examples of the hydrocarbon group having at least two —CH ₃ partial structures in the general formulas (CI) to (C-II) and R ₂ include an isopropyl group, an isobutyl group, t- Butyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2 , 3,5,7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group, isobornyl group and the like. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2,3-dimethyl-2-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5 , 7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group and isobornyl group.
Specific examples of the hydrocarbon group having at least two —CH ₃ partial structures in the general formula (C-III) and R ₂ include an isobutyl group, a t-butyl group, a 3-pentyl group, 2 , 3-dimethylbutyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, Isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4- Examples include heptyl group, 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group and the like. More preferably, it has more preferably 5 to 20 carbon atoms, and 2-methyl-3-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4. -Pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4 -Heptyl group, 2,6-dimethylheptyl group, 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group.

  The total content of the repeating units selected from the general formulas (CI) to (C-III) is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, based on all repeating units in the polymer.

  Preferable specific examples of the repeating unit represented by formula (CI) are listed below. Note that the present invention is not limited to this.

  Preferred specific examples of the repeating unit represented by formula (C-II) are shown below. Note that the present invention is not limited to this.

In general formula (C-III), when P ₂ is an oxygen atom, the carbon atom directly connected to the oxygen atom is preferably secondary or tertiary.
Specific preferred examples of the repeating unit represented by formula (C-III) are shown below. Note that the present invention is not limited to this. In specific examples, Rx represents a hydrogen atom or a methyl group, and Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms.

The resin of component (C) does not have a silicon atom or a fluorine atom.
The resin of component (C) preferably has no elements other than carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms and sulfur atoms.

It is preferable that the resin of the component (C) further contains a repeating unit represented by the following general formula (C).

In general formula (C),
X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom, an alkyl group or a halogen atom.
L represents a single bond or a divalent linking group.
Rp ₁ represents an acid-decomposable group.

  The repeating unit represented by the general formula (C) is preferably a repeating unit represented by the following general formula (C1).

In general formula (C1),
X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom, an alkyl group or a halogen atom.
R ₁₂ , R ₁₃ and R ₁₄ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. However, at least one of R ₁₂ , R ₁₃ and R ₁₄ represents an alkyl group. Two of R ₁₂ , R ₁₃ and R ₁₄ may combine to form a ring.

By containing the hydrophobic resin (HR), the hydrophobic resin (HR) is unevenly distributed on the surface of the photosensitive film, and when the immersion medium is water, the photosensitive film surface recedes with respect to water when the photosensitive film is formed. The contact angle can be improved and the immersion water followability can be improved.
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 photosensitive film formed using the photosensitive composition of the present invention is preferably 60 ° to 90 °, more preferably 70 ° or more.
The addition amount of the hydrophobic resin (HR) can be adjusted as appropriate so that the receding contact angle of the photosensitive film falls within the above range, but it is 0.1 to 10 mass based on the total solid content of the photosensitive composition. %, And more preferably 0.1 to 5% by mass.
The receding contact angle defined here is the receding contact angle measured by the expansion and contraction method. Specifically, it can be measured using a fully automatic contact angle meter (manufactured by Kyowa Interface Science / DM700) on a silicon wafer. After 36 μL of water droplets were prepared with a syringe on the positive resist composition prepared in (1), the water was sucked at a speed of 6 μL / sec, and the contact angle during suction showed a stable value.

  Hydrophobic resin (HR) is ubiquitous at the interface as described above, but unlike surfactant (E), it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances are homogeneous. It is not necessary to contribute to mixing.

Furthermore, the resin (HR) may contain 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

(X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imide groups Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group Groups and the like.
Preferable alkali-soluble groups include a sulfonimide group and a bis (carbonyl) methylene group.

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. It is preferable to use a repeating unit in which an alkali-soluble group is bonded to the chain, and further introduce a polymerization initiator or chain transfer agent having an alkali-soluble group at the end of the polymer chain at the time of polymerization.
The content of the repeating unit having an alkali-soluble group (x) is preferably from 0 to 20 mol%, more preferably from 0 to 10 mol%, based on all repeating units in the polymer.

  Specific examples of the repeating unit having an alkali-soluble group (x) are shown below.

(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, an acid imide group, and the like, and preferably a lactone structure It is group which has.
The repeating unit having a group (y) that is decomposed by the action of an alkali developer and increases the solubility in the alkali developer includes a resin via a linking group such as a repeating unit of an acrylate ester or a methacrylate ester. A polymerization initiator or chain transfer agent having a repeating unit in which an alkali-soluble group is bonded to the main chain or a group (y) that increases solubility in an alkaline developer is introduced at the end of the polymer chain during polymerization. Both are preferable.
The content of the repeating unit having a group (y) whose solubility in an alkali developer increases is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, based on all repeating units in the polymer.

  Specific examples of the repeating unit having a group (y) that increases the solubility in an alkali developer are shown below.

  (Z) Examples of the group capable of decomposing by the action of an acid include the same acid-decomposable groups as mentioned for the resin (A). The content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably 0 to 100 mol%, more preferably 0 to 80 mol%, still more preferably 0 to 50 mol%, based on all repeating units in the polymer. It is.

  The content of the component (C) resin is 0.1 to 20% by mass, more preferably 0.1 to 20% by mass, based on the solid content of the positive resist composition (total solid content constituting the resist film). It is 10 mass%, More preferably, it is 0.1-5 mass%.

  The weight average molecular weight of the resin (HR) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 3,000 to 15,000. The resin of component (C) preferably has a dispersity (Mw / Mn) of 1.0 to 3.0, more preferably 1.2 to 2.5, and even more preferably 1.2 to 2. .0.

  As with the acid-decomposable resin (A), the resin (HR) preferably has 0 to 10% by mass of residual monomer and oligomer components, and more preferably has few impurities such as metals. 0-5 mass% and 0-1 mass% are still more preferable. 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 1 to 5, more preferably 1 to 3, in terms of resolution, resist shape, resist pattern side wall, roughness, and the like.

  As the 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 that used in the resist 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 the polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) can be used to start the polymerization, and a chain transfer agent can be used if necessary. 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 is 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. 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 resin are shown below. The following table shows the molar ratio of 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 coming into direct contact with the immersion liquid between the resist film made of the resist composition of the present invention and the immersion liquid, an immersion liquid hardly soluble film (hereinafter also referred to as “top coat”) is provided. It may be provided. The functions necessary for the top coat are suitability for application to the upper layer of the resist, transparency to radiation, particularly 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 photosensitive film is preferable. In terms that the peeling step can be performed simultaneously with the development processing step of the photosensitive film, it is preferable that the peeling step can be performed with an alkali developer. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the photosensitive 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 photosensitive film and further not mixed with the immersion liquid.
From this viewpoint, when the immersion liquid is water, the solvent used for the topcoat is preferably a non-water-soluble medium that is hardly soluble in the solvent used for the photosensitive composition. Furthermore, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

(D) Solvent The photosensitive composition of the present invention is used by dissolving the above components in a predetermined solvent.

  The solvent that can be used is usually an organic solvent. Examples of the solvent include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- Methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate Propylpyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran And the like can be given.

In the present invention, the organic solvent may be used alone or in combination, but it is preferable to use a mixed solvent containing two or more solvents having different functional groups. As a result, the solubility of the material is increased, and not only the generation of particles over time can be suppressed, but also a good pattern profile can be obtained. Preferable functional groups contained in the solvent include ester groups, lactone groups, hydroxyl groups, ketone groups, and carbonate groups. As the mixed solvent having different functional groups, the following mixed solvents (S1) to (S5) are preferable.
(S1) a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group,
(S2) Mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed (S3) A mixed solvent in which a solvent having an ester structure and a solvent having a lactone structure are mixed (S4) A solvent having an ester structure and a lactone Mixed solvent in which solvent having structure and solvent containing hydroxyl group are mixed (S5) Mixed solvent in which solvent having ester structure, solvent having carbonate structure and solvent containing hydroxyl group are mixed. Generation | occurrence | production can be reduced and generation | occurrence | production of the defect at the time of application | coating can be suppressed.

  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 and cyclohexanone are most preferred.

Examples of the solvent having a ketone structure include cyclohexanone and 2-heptanone, and cyclohexanone is preferable.
Examples of the solvent having an ester structure include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, and butyl acetate, and propylene glycol monomethyl ether acetate is preferable.
Examples of the solvent having a lactone structure include γ-butyrolactone.
Examples of the solvent having a carbonate structure include propylene carbonate and ethylene carbonate, with propylene carbonate being preferred.

  The resist composition of the present invention preferably contains at least one of propylene glycol monomethyl ether acetate, 2-heptanone, and γ-butyrolactone.

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 mixing ratio (mass) of the solvent having an ester structure and the solvent having a ketone structure is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 40/60 to 80/20. . A mixed solvent containing 50% by mass or more of a solvent having an ester structure is particularly preferable from the viewpoint of coating uniformity.
The mixing ratio (mass) of the solvent having an ester structure and the solvent having a lactone structure is 70/30 to 99/1, preferably 80/20 to 99/1, and more preferably 90/10 to 99/1. . A mixed solvent containing 70% by mass or more of a solvent having an ester structure is particularly preferable from the viewpoint of stability over time.
When mixing a solvent having an ester structure, a solvent having a lactone structure, and a solvent containing a hydroxyl group, the solvent having an ester structure is 30 to 80% by weight, the solvent having a lactone structure is 1 to 20% by weight, and the hydroxyl group is contained. It is preferable to contain 10 to 60% by weight of the solvent.
When mixing a solvent having an ester structure, a solvent having a carbonate structure and a solvent containing a hydroxyl group, the solvent having an ester structure is 30 to 80% by weight, the solvent having a carbonate structure is 1 to 20% by weight, and the hydroxyl group is contained. It is preferable to contain 10 to 60% by weight of the solvent.

(E) Basic compound The positive photosensitive composition of the present invention comprises (E) a base in order to reduce the change in performance over time from exposure to heating, or to control the diffusibility of the acid generated by exposure in the film. It is preferable to contain a functional compound.

Examples of basic compounds include nitrogen-containing basic compounds and onium salt compounds.
Preferable nitrogen-containing basic compound structures include compounds having partial structures represented by the following formulas (A) to (E).

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl having 1 to 20 carbons, a cycloalkyl group having 3 to 20 carbons or an aryl group having 6 to 20 carbons, R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. A 20 hydroxyalkyl group or a C 3-20 hydroxycycloalkyl group is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.

  Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, and may have a substituent. More preferable compounds include compounds having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, a hydroxyl group and / or Or the aniline derivative which has an ether bond etc. can be mentioned.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. 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. ] Undec-7-ene. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety 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 aniline compounds include 2,6-diisopropylaniline and N, N-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.
The resist composition of the present invention preferably contains at least one of 2,6-diisopropylaniline and tetrabutylammonium hydroxide.

  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 based on solid content of a positive photosensitive composition, Preferably it is 0.01-5 mass%. In order to obtain a sufficient addition effect, 0.001% by mass or more is preferable, and 10% by mass or less is preferable in terms of sensitivity and developability of the non-exposed area.

(F) Surfactant The positive photosensitive composition of the present invention preferably contains a surfactant. As the surfactant, any one of fluorine-based and / or silicon-based surfactants (fluorine-based surfactant and silicon-based surfactant, surfactant containing both fluorine atom and silicon atom), or two kinds of surfactants It is preferable to contain the above.

  When the positive photosensitive composition of the present invention contains fluorine and / or a silicon-based surfactant, adhesion and development with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. A resist pattern with few defects can be provided.

  Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 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 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. 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. It 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 ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. Can.

  Other surfactants other than fluorine and / or silicon surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan aliphatic esters And nonionic surfactants such as polyoxyethylene sorbitan aliphatic esters.

  These surfactants may be added alone or in some combination.

  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 positive photosensitive composition (excluding the solvent).

(G) A dissolution control compound having a molecular weight of 3000 or less (hereinafter also referred to as a “solubility control compound”) having at least one selected from an alkali-soluble group, a hydrophilic group, and an acid-decomposable group may be added. Control compounds include carboxyl groups, sulfonylimide groups, compounds having an alkali-soluble group such as a hydroxyl group substituted at the α-position with a fluoroalkyl group, hydroxyl groups, lactone groups, cyano groups, amide groups, pyrrolidone groups, sulfonamide A compound having a hydrophilic group such as a group or a compound containing a group capable of decomposing by the action of an acid to release an alkali-soluble group or a hydrophilic group is preferable. The group capable of decomposing by the action of an acid to release an alkali-soluble group or a hydrophilic group is preferably a group in which a carboxyl group or a hydroxyl group is protected with an acid-decomposable group. In order not to lower the permeability of 220 nm or less as the dissolution control compound, it is preferable to use a compound that does not contain an aromatic ring, or to use a compound having an aromatic ring in an amount of 20 wt% or less based on the solid content of the composition.
Preferred dissolution control compounds include carboxylic acid compounds having an alicyclic hydrocarbon structure such as adamantane (di) carboxylic acid, norbornane carboxylic acid, and cholic acid, or compounds in which the carboxylic acid is protected with an acid-decomposable group, and polyols such as saccharides. Or a compound having its hydroxyl group protected with an acid-decomposable group is preferred.

  The molecular weight of the dissolution controlling 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 control compound is preferably 3 to 40% by mass, more preferably 5 to 20% by mass, based on the solid content of the photosensitive composition.

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

<Other additives>
If necessary, the positive photosensitive composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a compound that promotes solubility in a developer, and the like.

  The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable.

  A preferable addition amount of these dissolution promoting compounds is 2 to 50% by mass, and more preferably 5 to 30% by mass with respect to the acid-decomposable resin. 50 mass% or less is preferable at the point of development residue suppression and the pattern deformation prevention at the time of image development.

  Such phenolic compounds having a molecular weight of 1000 or less can be obtained by referring to methods described in, for example, JP-A-4-1222938, JP-A-2-28531, U.S. Pat. No. 4,916,210, European Patent 219294, and the like. Can be easily synthesized.

  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 formation method)
The positive photosensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and applying the solution on a predetermined support as follows. The filter used for filter filtration is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 microns or less, more preferably 0.05 microns or less, and still more preferably 0.03 microns or less.

For example, a positive photosensitive composition is coated on a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of precision integrated circuit elements by a suitable coating method such as a spinner or coater, dried, and photosensitive. A film is formed.
The photosensitive 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.
It is preferable to perform exposure (immersion exposure) by filling a liquid (immersion medium) having a refractive index higher than air between the photosensitive film and the lens during irradiation with actinic rays or radiation. 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. Further, an overcoat layer may be further provided on the photosensitive film so that the immersion medium and the photosensitive film do not come into direct contact with each other during the immersion exposure. Thereby, the elution of the composition from the photosensitive film to the immersion medium is suppressed, and development defects are reduced.

Before forming the photosensitive 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.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, etc., but preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. 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) An electron beam is preferred.

In the development step, an alkaline developer is used as follows. As an alkaline developer of the resist composition, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as quaternary ammonium salts, 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

Synthesis Example Synthesis of Resin (C) 25.63 g of tert-butyl acrylate was dissolved in propylene glycol monomethyl ether acetate to prepare 117.92 g of a solution having a solid content concentration of 20%. To this solution, 2.0 mol% (0.921 g) of a polymerization initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added, and this was heated to 80 ° C. for 4 hours under a nitrogen atmosphere. To 25 g. After completion of dropping, the reaction solution was stirred at 80 ° C. for 2 hours. The reaction solution was cooled to room temperature and added dropwise to 20 times the amount of methanol. The precipitated solid was filtered to obtain 22.1 g of the target resin HR-1.
The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 12000, and the degree of dispersion was 2.0.
Similarly, another resin (C) was prepared.

<Registration adjustment>
The components shown in Table 2 below were dissolved in a solvent, and a solution having a solid content of 7% by mass was prepared for each, and this was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare a positive resist solution. The prepared positive resist composition was evaluated by the following method, and the results are shown in the following table.
In addition, about each component in a table | surface, ratio when using two or more is a mass ratio.

[Image performance test]
(Condition 1)
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 a 78 nm antireflection film. The positive resist composition prepared thereon was applied, and baked at 120 ° C. for 60 seconds to form a 250 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (PAS5500 / 1100, NA0.75, σo / σi = 0.85 / 0.55, manufactured by ASML). Thereafter, heating was performed at 120 ° 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.

(Condition 2)
This condition is to form a resist pattern by an immersion exposure method using pure water.
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 a 78 nm antireflection film. The positive resist composition prepared thereon was applied, and baked at 120 ° C. for 60 seconds to form a 250 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser immersion scanner (NA 0.75). As the immersion liquid, ultrapure water having impurities of 5 ppb or less was used. Thereafter, heating was performed at 120 ° 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.

[Line edge roughness evaluation]
The line edge edge roughness (LER) is measured by using a length-measuring scanning electron microscope (SEM) to observe an isolated pattern of 120 nm and from the reference line where the edge in the longitudinal direction of the line pattern should be 5 μm. The distance was measured by 50 points with a length measuring SEM (Hitachi, Ltd. S-8840), the standard deviation was obtained, and 3σ was calculated. The unit is nm, and a smaller value indicates better performance.

[Water followability]
The prepared positive resist composition was applied on a silicon wafer and baked at 115 ° C. for 60 seconds to form a 200 nm resist film. Next, as shown in FIG. 1, 15 ml of distilled water was pipetted on the center of the wafer 1 on which the obtained resist film was formed. A 10 cm square quartz plate 3 with a string 2 was placed on the distilled water paddle so that the entire gap between the wafer 1 and the quartz plate 3 was filled with distilled water 4.
Next, the thread 2 attached to the quartz plate 3 with the wafer 1 fixed is wound around the rotating part of the motor 5 that rotates at a speed of 30 cm / second, and the motor 5 is switched on for 0.5 seconds to turn on the quartz plate 3. Moved. After the movement of the quartz plate 3, the amount of distilled water remaining under the quartz plate 3 was judged according to the following criteria, and used as an index of water followability.
2, (a) to (d) schematically show various patterns obtained by observing the quartz plate 3 from above after the quartz plate is moved, and the hatched portion 6 remains below the quartz plate 3. The blank space 7 is an area where the distilled water cannot follow the movement of the quartz plate 3 and the air has entered.
As shown in (a), the water remains on the entire surface of the substrate even after moving the quartz plate, and the followability is excellent. As shown in (b), the area where air enters is about 10% of the total substrate area. Followability ○, as shown in (c), the area where the air enters is 20% or more and less than 50% of the total board area △, the area where the air enters as shown in (d) The thing of 50% or more with respect to the board | substrate area was made into followable | trackability x.

  The symbols in Table 2 are as follows.

  The structure of the acid-decomposable resin (A) used in the examples is shown below.

  The structure of the compound (B) used in the examples is shown below.

N-1: N, N-dibutylaniline N-2: Tetrabutylammonium hydroxide N-3: 2,6-diisopropylaniline N-4: Tri-n-octylamine N-5: N, N-dihydroxyethylaniline N-6: N, N-dihexylaniline

W-1: Megafuck F176 (manufactured by Dainippon Ink & Chemicals, Inc.)
(Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.)
(Fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Silicon)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: PF656 (manufactured by OMNOVA, fluorine-based)
W-6: PF6320 (manufactured by OMNOVA, fluorine-based)

SL-1: cyclohexanone SL-2: propylene glycol monomethyl ether acetate SL-3: 2-heptanone SL-4: propylene glycol monomethyl ether SL-5: γ-butyrolactone SL-6: propylene carbonate

  From the results shown in Table 2, it is clear that the photosensitive composition of the present invention has excellent water followability and good line edge roughness during immersion exposure.

The schematic diagram (side view) regarding water follow-up evaluation. The schematic diagram (upper surface) regarding evaluation of water followability.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Wafer which formed resist film 2 Thread 3 Quartz board 4 Distilled water 5 Motor 6 Area with distilled water 7 Area with air

Claims (16)

(A) a resin having an acid-decomposable repeating unit represented by the following general formula (I), which increases the dissolution rate in an alkali developer by the action of an acid; (B) an acid by irradiation with actinic rays or radiation; A generated compound, (C) a resin that does not contain fluorine and silicon and has at least one repeating unit selected from the following general formulas (CI) to (C-III), and (D) a solvent A positive photosensitive composition, wherein the content of the resin of component (C) is 0.1 to 20% by mass based on the solid content of the positive resist composition .

In general formula (I),
Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
Ry _{1 to} Ry ₃ each independently represents an alkyl group or a cycloalkyl group. At least two members out of Ry _{1 to} Ry ₃ may be bonded to form a ring structure.
Z represents a divalent linking group .

In formulas (CI) to (C-III),
R ₁ each independently represents a hydrogen atom or a methyl group.
R ₂ each independently represents a hydrocarbon group having one or more —CH ₃ partial structures.
P ₁ represents a single bond or alkylene, ether, or a linking group having two or more thereof.
P ₂ represents a linking group selected from —O—, —NR— (R is a hydrogen atom or alkyl), and —NHSO ₂ —.
n represents an integer of 1 to 4 .   The positive resist composition according to claim 1, wherein Z in the general formula (I) is a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group.   The positive resist composition according to claim 1 or 2, wherein Z in the general formula (I) is a divalent chain hydrocarbon group. The positive resin according to any one of claims 1 to 3, wherein the resin of component (A) further has a repeating unit having at least one kind selected from a lactone group, a hydroxyl group, a cyano group, and an acid group. Resist composition. As the component (B), the positive resist composition according to any one of claims 1 to 4, characterized in that a compound capable of generating an acid represented by the following general formula (BII).

In general formula (BII),
Rb ₁ represents a group having an electron-withdrawing group.
Rb ₂ represents an organic group having no electron withdrawing group.
m and n each represents an integer of 0 to 5. However, m + n ≦ 5.
When m is 2 or more, a plurality of Rb ₁ may be the same or different.
When n is 2 or more, a plurality of Rb ₂ may be the same or different. In general formula (BII), m is 1 to 5, and the electron-withdrawing group of Rb ₁ is at least one selected from a fluorine atom, a fluoroalkyl group, a nitro group, an ester group, and a cyano group. The positive resist composition according to claim 5 . The resin of component (C), further characterized by containing a repeating unit represented by the following general formula (C), the positive resist composition according to any one of claims 1-6.

In general formula (C),
X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom, an alkyl group or a halogen atom.
L represents a single bond or a divalent linking group.
Rp ₁ represents an acid-decomposable group. The positive resist composition according to claim 7 , wherein the repeating unit represented by the general formula (C) is a repeating unit represented by the following general formula (C1).

In general formula (C1),
X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom, an alkyl group or a halogen atom.
R ₁₂ , R ₁₃ and R ₁₄ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. However, at least one of R ₁₂ , R ₁₃ and R ₁₄ represents an alkyl group. Two of R ₁₂ , R ₁₃ and R ₁₄ may combine to form a ring.   In the general formulas (CI) to (C-III), R ₂ Is -CH ₃ The positive resist composition according to claim 1, wherein the positive resist composition has two or more partial structures.   Component (C) is selected from (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, and (z) a group that decomposes by the action of an acid. The positive resist composition according to claim 1, wherein the positive resist composition has at least one group. The total content of at least one repeating unit selected from the general formulas (CI) to (C-III) is 80 to 100 mol% with respect to all repeating units in the resin of the component (C). The positive resist composition according to claim 1.   12. The positive type according to claim 1, wherein the content of the resin of component (C) is 0.1 to 10% by mass based on the solid content of the positive type resist composition. Resist composition. The positive resist composition according to any one of claims 1 to 12 wavelengths is characterized by using the following exposure 200 nm.   A resist film formed from the positive resist composition according to claim 1. It claims 1-4 EXPOSURE Les resist film according to a pattern forming method characterized by comprising the step of developing. The pattern forming method according to claim 15 , wherein the resist film is exposed through an immersion liquid.

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