JP4682069B2 - Positive photosensitive composition and pattern forming method using the same - Google Patents

Description

  The present invention relates to a positive photosensitive composition whose properties change upon reaction with irradiation of actinic rays or radiation, and a pattern forming method using the positive photosensitive composition. More specifically, a positive photosensitive composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, a further photofabrication process, a lithographic printing plate, an acid curable composition, and the like The present invention relates to a pattern forming method using a positive photosensitive composition.

  The chemically amplified photosensitive composition generates an acid in the exposed area by irradiation with actinic light or radiation such as far ultraviolet light, and develops the irradiated part and non-irradiated part of the active light or radiation by a reaction using this acid as a catalyst. It is a pattern forming material that changes the solubility in a liquid and forms a pattern on a substrate.

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

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

  Various improvements have also been made on acid-decomposable resins that are main constituents of chemically amplified resist compositions. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2004-53822) discloses specific methacrylic repeating units. An acid-decomposable resin having is disclosed.

  However, a sufficient effect has not been obtained yet, and further improvement of the line width roughness (LWR) is desired.

JP 2004-53822 A

  Accordingly, an object of the present invention is to provide a positive photosensitive composition capable of obtaining excellent line width roughness (LWR) performance and a pattern forming method using the positive photosensitive composition. is there.

一般式（ｐ２−Ｉ）中、
Ｒ _２１１ はアルキル基を示し、
Ｚ２は炭素原子とともに単環式アルキル基を形成するのに必要な原子団を示す。

一般式（Ｌ−１）、（Ｌ−２）中、
Ｒ _Ｌ１ は水素原子又はアルキル基を示す。
Ｒ _Ｌ４ は複数ある場合は各々独立してアルキル基又はシアノ基を示す。
ｎは１以上の整数を表す。
Ｒ _Ｌ２ は水素原子又はアルキル基を示す。
ＬＺ２はラクトン環の炭素原子２個とともに環を形成するのに必要な原子団を表す。
２．
多環式脂肪族基が、一般式（p１−Ｉ）又は（p１−ＩＩ）で表されることを特徴とする上記１に記載のポジ型感光性組成物。

一般式（ｐ１−Ｉ）中、
Ｒ _１１１ はアルキル基を示し、
Ｚ１は炭素原子とともに多環式アルキル基を形成するのに必要な原子団を示す。
一般式（ｐ１−ＩＩ）中、
Ｒ _１１２ 、Ｒ _１１３ は各々独立してアルキル基を示す。
Ｒ _１１４ は多環式アルキル基を示す。
３．
多環式脂肪族基が、前記一般式（p１−Ｉ）で表されることを特徴とする上記２に記載のポジ型感光性組成物。
４．
一般式（ｐ１−Ｉ）におけるＺ１が炭素原子とともに形成する多環式アルキル基が２−アダマンチル基、２−ノルボルニル基のいずれかであるか、または、一般式（ｐ１−ＩＩ）におけるＲ _１１４ としての多環式アルキル基が、１−アダマンチル基であることを特徴とする上記２に記載のポジ型感光性組成物。
５．
前記一般式（ｐ２−Ｉ）におけるＺ２が炭素原子とともに形成する単環式アルキル基がシクロヘキシル基、シクロペンチル基のいずれかであることを特徴とする上記１〜４のいずれか１項に記載のポジ型感光性組成物。
６．
単環式脂肪族基を有する繰り返し単位が下記一般式７で表されることを特徴とする上記１〜５のいずれか１項に記載のポジ型感光性組成物。

一般式７中、
ＲｘはＣＨ _３ 、ＣＦ _３ 、またはＣＨ _２ ＯＨを表す。
Ｒｘａは炭素数１〜４のアルキル基を表す。
７．
（Ｂ１）の樹脂が、ラクトン基を有することを特徴とする上記１〜６のいずれか１項に記載のポジ型感光性組成物。
８．
ラクトン基が下記一般式ＬＣ１−４で表されることを特徴とする上記７に記載のポジ型感光性組成物。

一般式ＬＣ１−４中、
Ｒｂ ₂ は、炭素数１〜８のアルキル基またはシアノ基を表す。
ｎ ₂ は０〜２の整数を表す。
ｎ ₂ が２以上の時、複数存在するＲｂ ₂ は同一でも異なっていてもよく、また、複数存在するＲｂ ₂ 同士が結合して環を形成してもよい。
９．
上記１〜８のいずれか１項に記載のポジ型感光性組成物により形成した感光性膜。
１０．
上記９に記載の感光性膜を、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。
尚、本発明は上記１〜１０の構成を有するものであるが、以下、その他についても参考のため記載した。 The present invention is as follows.
1.
(A) a compound that generates an acid upon irradiation with an actinic ray or radiation,
(B1) a resin containing a repeating unit having a polycyclic aliphatic group that decomposes with an acid to generate an alkali-soluble group, and
(B2) A monocyclic aliphatic represented by the repeating unit represented by the following general formula (L-1) or (L-2) and the general formula (p2-I) that decomposes with an acid to generate an alkali-soluble group A positive photosensitive composition comprising a resin containing a repeating unit having a group.

In general formula (p2-I),
R ₂₁₁ represents an alkyl group,
Z2 represents an atomic group necessary for forming a monocyclic alkyl group together with a carbon atom.

In general formulas (L-1) and (L-2),
R _L1 represents a hydrogen atom or an alkyl group.
When there are a plurality of R _{L4 s,} each independently represents an alkyl group or a cyano group.
n represents an integer of 1 or more.
R _L2 represents a hydrogen atom or an alkyl group.
LZ2 represents an atomic group necessary for forming a ring together with two carbon atoms of the lactone ring.
2.
2. The positive photosensitive composition as described in 1 above, wherein the polycyclic aliphatic group is represented by the general formula (p1-I) or (p1-II).

In general formula (p1-I),
R ₁₁₁ represents an alkyl group,
Z1 represents an atomic group necessary for forming a polycyclic alkyl group together with a carbon atom.
In general formula (p1-II),
R ₁₁₂ and R ₁₁₃ each independently represents an alkyl group.
R ₁₁₄ represents a polycyclic alkyl group.
3.
3. The positive photosensitive composition as described in 2 above, wherein the polycyclic aliphatic group is represented by the general formula (p1-I).
4).
Polycyclic alkyl group is 2-adamantyl group Z1 in the general formula (p1-I) is formed together with a carbon atom, or either of the 2-norbornyl radical, or, as _{R 114} in formula (p1-II) 3. The positive photosensitive composition as described in 2 above, wherein the polycyclic alkyl group is a 1-adamantyl group.
5.
5. The positive electrode according to any one of 1 to 4 above, wherein the monocyclic alkyl group formed by Z2 together with the carbon atom in the general formula (p2-I) is a cyclohexyl group or a cyclopentyl group. Type photosensitive composition.
6).
6. The positive photosensitive composition as described in any one of 1 to 5 above, wherein the repeating unit having a monocyclic aliphatic group is represented by the following general formula 7.

In general formula 7,
Rx represents CH ₃ , CF ₃ , or CH ₂ OH.
Rxa represents an alkyl group having 1 to 4 carbon atoms.
7).
7. The positive photosensitive composition as described in any one of 1 to 6 above, wherein the resin (B1) has a lactone group.
8).
8. The positive photosensitive composition as described in 7 above, wherein the lactone group is represented by the following general formula LC1-4.

In general formula LC1-4,
Rb ₂ represents an alkyl group or a cyano group having 1 to 8 carbon atoms.
n ₂ represents an integer of 0 to 2.
When n ₂ 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.
9.
A photosensitive film formed from the positive photosensitive composition according to any one of 1 to 8 above.
10.
10. A pattern forming method comprising the steps of exposing and developing the photosensitive film according to 9 above.
In addition, although this invention has the structure of said 1-10, hereafter, it described for reference also about others.

一般式（Ｌ−１）、（Ｌ−２）中、
Ｒ_Ｌ１は水素原子又はアルキル基を示す。
Ｒ_Ｌ４は複数ある場合は各々独立してアルキル基又はシアノ基を示す。
ｎは１以上の整数を表す。
Ｒ_Ｌ２は水素原子又はアルキル基を示す。
ＬＺ２はラクトン環の炭素原子２個とともに環を形成するのに必要な原子団を表す。
＜２＞
多環式脂肪族基が、一般式（p１−Ｉ）又は（p１−ＩＩ）で表されることを特徴とする上記＜１＞に記載のポジ型感光性組成物。

一般式（ｐ１−Ｉ）中、
Ｒ_１１１はアルキル基を示し、
Ｚ１は炭素原子とともに多環式アルキル基を形成するのに必要な原子団を示す。
一般式（ｐ１−ＩＩ）中、
Ｒ_１１２、Ｒ_１１３は各々独立してアルキル基を示し、
Ｒ_１１４は多環式アルキル基を示す。
＜３＞
単環式脂肪族基が、一般式（p２−Ｉ）又は（p２−ＩＩ）で表されることを特徴とする上記＜１＞または＜２＞に記載のポジ型感光性組成物。

一般式（ｐ２−Ｉ）中、
Ｒ_２１１はアルキル基を示し、
Ｚ２は炭素原子とともに単環式アルキル基を形成するのに必要な原子団を示す。
一般式（ｐ２−ＩＩ）中、
R_２１２及びＲ_２１３は各々独立してアルキル基を示し、
Ｒ_２１４は単環式アルキル基を示す。
＜４＞
一般式（ｐ１−Ｉ）で表される多環式脂肪族基が２−アダマンチル基、２−ノルボルニル基のいずれかであるか、または、一般式（ｐ１−ＩＩ）で表される多環式脂肪族基が、１−アダマンチル基であることを特徴とする上記＜１＞〜＜３＞のいずれかに記載のポジ型感光性組成物。
＜５＞
一般式（ｐ２−Ｉ）で表される単環式脂肪族基がシクロヘキシル基、シクロペンチル基のいずれかであるか、または一般式（ｐ２−ＩＩ）で表される単環式脂肪族基がシクロヘキシル基、シクロペンチル基、４−メチル−１−シクロヘキシル基のいずれかであることを特徴とする上記＜１＞〜＜４＞のいずれかに記載のポジ型感光性組成物。
＜６＞
上記＜１＞〜＜５＞のいずれかに記載のレジスト組成物によりレジスト膜を形成し、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。 <1>
(A) a compound that generates an acid upon irradiation with an actinic ray or radiation,
(B1) a resin containing a repeating unit having a polycyclic aliphatic group that decomposes with an acid to generate an alkali-soluble group, and
(B2) A resin containing a repeating unit represented by the following general formula (L-1) or (L-2) and a repeating unit having a monocyclic aliphatic group that decomposes with an acid to generate an alkali-soluble group ,
A positive photosensitive composition comprising:

In general formulas (L-1) and (L-2),
R _L1 represents a hydrogen atom or an alkyl group.
When there are a plurality of R _{L4 s,} each independently represents an alkyl group or a cyano group.
n represents an integer of 1 or more.
R _L2 represents a hydrogen atom or an alkyl group.
LZ2 represents an atomic group necessary for forming a ring together with two carbon atoms of the lactone ring.
<2>
The positive photosensitive composition as described in <1> above, wherein the polycyclic aliphatic group is represented by the general formula (p1-I) or (p1-II).

In general formula (p1-I),
R ₁₁₁ represents an alkyl group,
Z1 represents an atomic group necessary for forming a polycyclic alkyl group together with a carbon atom.
In general formula (p1-II),
R ₁₁₂ and R ₁₁₃ each independently represents an alkyl group,
R ₁₁₄ represents a polycyclic alkyl group.
<3>
The positive photosensitive composition as described in <1> or <2> above, wherein the monocyclic aliphatic group is represented by the general formula (p2-I) or (p2-II).

In general formula (p2-I),
R ₂₁₁ represents an alkyl group,
Z2 represents an atomic group necessary for forming a monocyclic alkyl group together with a carbon atom.
In general formula (p2-II),
R ₂₁₂ and R ₂₁₃ each independently represent an alkyl group,
R ₂₁₄ represents a monocyclic alkyl group.
<4>
The polycyclic aliphatic group represented by the general formula (p1-I) is either a 2-adamantyl group or 2-norbornyl group, or the polycyclic group represented by the general formula (p1-II) The positive photosensitive composition as described in any one of <1> to <3> above, wherein the aliphatic group is a 1-adamantyl group.
<5>
The monocyclic aliphatic group represented by the general formula (p2-I) is either a cyclohexyl group or a cyclopentyl group, or the monocyclic aliphatic group represented by the general formula (p2-II) is cyclohexyl. The positive photosensitive composition as described in any one of <1> to <4> above, which is any one of a group, a cyclopentyl group, and a 4-methyl-1-cyclohexyl group.
<6>
The pattern formation method characterized by including the process of forming a resist film with the resist composition in any one of said <1>-<5>, exposing and developing.

  According to the present invention, it is possible to provide a positive photosensitive composition excellent in line width roughness and a pattern forming method using the positive photosensitive composition.

Hereinafter, the present invention will be described in detail.
In addition, in the description of a group (atomic group) in this specification, the description which does not describe substituted and unsubstituted includes what has a substituent with the thing which does not have 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).

[1] (A) Compound that generates acid upon irradiation with actinic ray or radiation Compound that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generator”) used in the positive photosensitive composition of the present invention. Will be described below.
The acid generator used in the present invention can be selected from compounds generally used as an acid generator.
In other words, photoinitiators for photocationic polymerization, photoinitiators for radical photopolymerization, photodecolorants for dyes, photochromic agents, or active rays or radiations such as far ultraviolet rays and X-rays used in micro resists, etc. A known compound that generates an acid by irradiation and a mixture thereof can be appropriately selected and used.

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

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

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

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

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.

The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

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

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

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

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.

In the 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, and the rest may be an alkyl group or a cycloalkyl group.

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

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

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

  The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

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

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

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

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

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

  Examples of the aliphatic group in the aliphatic sulfonate anion include, for example, an alkyl group having 1 to 30 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec- Butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl And an eicosyl group and a cycloalkyl group having 3 to 30 carbon atoms, specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, and the like.

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

  The alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.

  Examples of such substituents include nitro groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), carboxyl groups, hydroxyl groups, amino groups, cyano groups, and alkoxy groups (preferably having 1 to 5 carbon atoms). ), A cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms). ), An alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  Examples of the aliphatic group in the aliphatic carboxylate anion include those similar to the aliphatic group in the aliphatic sulfonate anion.

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

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

  The aliphatic group, aromatic group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent include aliphatic sulfonic acid The same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group and the like as in the anion can be exemplified.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. These alkyl groups may have a substituent, and examples of the substituent include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, and the like, which are substituted with a fluorine atom. Alkyl groups are preferred.

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

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

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group not containing an aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

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

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear, branched, cyclic 2-oxoalkyl group, or an alkoxycarbonylmethyl group, most preferably Is a linear, branched 2-oxoalkyl group.

The alkyl group as R _{201 to} R ₂₀₃ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. Butyl group, pentyl group and the like. More preferable examples of the alkyl group include a 2-linear or branched oxoalkyl group and an alkoxycarbonylmethyl group.

The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cycloalkyl group having 3 to 10 carbon atoms, e.g., cyclopentyl, cyclohexyl group and a norbornyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

  The 2-oxoalkyl group may be linear, branched or cyclic, and preferably includes a group having> C═O at the 2-position of the above alkyl group or cycloalkyl group.

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

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

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

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

Any two or more of R _1c to R _7c, and R _x and R _y may be bonded to each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond May be included. Examples of the group formed by combining any two or more of R _{1c to} R _7c and R _x and R _y are a butylene group and a pentylene group.

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

The alkyl group as R _{1c to} R _7c is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, A linear or branched pentyl group can be exemplified.

The cycloalkyl group as R _{1c to} R _7c is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopentyl group and a 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, any one of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c is 2 ~ 15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl groups and cycloalkyl groups as R _{1c to} R _{7c, such} as a 2-oxoalkyl group and a 2-oxocycloalkyl group. An alkoxycarbonylmethyl group is more preferable.

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

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

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

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

The alkyl group as R ₂₀₄ to R ₂₀₇ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group.

The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably a cycloalkyl group having 3 to 10 carbon atoms, e.g., cyclopentyl, cyclohexyl group and a norbornyl group.

The R ₂₀₄ to R ₂₀₇ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (e.g., 6 carbon atoms 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.

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

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

In general formula (ZIV), two Ar ₃ each independently represents an aryl group.
R ₂₀₈ in the general formulas (ZV) and (ZVI) each independently represents an alkyl group, a cycloalkyl group or an aryl group, and the alkyl groups as R _{204 to} R ₂₀₇ in the general formulas (ZI) to (ZIII) , Cycloalkyl group or aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

  Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.

  As the acid generator in the present invention, particularly preferably, an anion structure containing an alkyl group having 4 or less carbon atoms substituted with a fluorine atom, a cycloalkyl group substituted with a fluorine atom, or an aromatic group substituted with a fluorine atom; An acid generator having a triarylsulfonium cation structure. Such acid generators are preferably those represented by the following general formulas (B1) to (B3).

In general formulas (B1) to (B3),
R ₁ represents an alkyl group, an alicyclic hydrocarbon group, a hydroxyl group, a carboxyl group, an alkoxy group or a halogen atom.
y represents 0 or an integer of 1 to 5 independently of each other. When y is an integer of 2 or more, two or more R _{1 s} may be the same or different.
Q _{1 to} Q ₄ are each independently an alkyl group having 1 to 8 carbon atoms substituted with a fluorine atom, a cycloalkyl group substituted with a fluorine atom, an aryl group substituted with a fluorine atom, or a fluorinated alkyl group. Represents a substituted aryl group.
In particular, in the general formula (B2), Q ₂ and Q _{3 which} are bonded to form a ring structure are preferable from the viewpoint of improving exposure latitude.

As the alkyl group for R ₁ , a linear or branched alkyl group having 1 to 15 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. Can be mentioned.
The alicyclic hydrocarbon group for R ₁ is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
The alkyl group substituted with a fluorine atom Q ₁ to Q _4, for _{example, -CF 3, -C 2 F 5} , -n-C 3 F 7, -n-C 4 F 9, -n-C 8 _{F 17, -CF (CF 3)} 2, -CH (CF 3) 2, - (CF 2) 2 OCF 2 CF 3, - (CF 2) 2 O (CH 2) 3 CH 3, - (CF 2) _{2 O (CH 2) 13 CH} 3, - (CF 2) 2 O (CF 2) 2 (CH 2) 3 CH 3 and the like. The alkyl group having 4 or less carbon atoms substituted with a fluorine atom of Q _{1 to} Q ₄ may further have a substituent such as an alkoxy group or a fluoroalkoxy group.
Examples of the aryl group substituted with a fluorine atom of Q _{1 to} Q ₄ include 2,3,4,5,6-pentafluorophenyl group, 2,3,4-trifluorophenyl group, and 2,4-difluoro. A phenyl group, 4-fluorophenyl group, 4-undecanyloxy-2,3,5,6-tetrafluorophenyl group and the like can be mentioned.
Examples of the aryl group substituted with a fluorinated alkyl group of Q _{1 to} Q ₄ include a 3-trifluoromethylphenyl group, a 3,5-bis (trifluoromethyl) phenyl group, a 4-trifluoromethylphenyl group, And 4-n-nonafluorobutylphenyl group.

  Examples of particularly preferable acid generators are given below.

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

[2] Resin (B1) containing a repeating unit having a polycyclic aliphatic group that decomposes with an acid to produce an alkali-soluble group

  The positive photosensitive composition of the present invention decomposes with an acid to produce an alkali-soluble group, that is, contains an acid-decomposable repeating unit having a polycyclic aliphatic group, and is soluble in an alkali developer by the action of an acid. (Hereinafter, also referred to as “acid-decomposable resin (B1)” or “resin (B1)”).

  The resin (B1) contains at least one selected from the group of repeating units having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (p1-I) to general formula (p1-V) It is preferable to be a resin. Among these, a resin containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (p1-I) or general formula (p1-II) is more preferable.

In general formulas (p1-I) to (p1-V),
R ₁₁₁ represents an alkyl group, and preferably represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group,
Z1 represents an atomic group necessary for forming a polycyclic alkyl group together with the carbon atoms to which Z1 is bonded.
R _{112 to} R ₁₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms, preferably an alkyl group. In addition, at least one of R _{112 to} R ₁₁₄ or any of R ₁₁₅ and R ₁₁₆ represents a polycyclic alkyl group.
R _{117 to} R ₁₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{117 to} R ₁₂₁ is a large number. Represents a cyclic alkyl group. Further, either R ₁₁₉ or R ₁₂₁ represents a linear or branched alkyl group or polycyclic alkyl group having 1 to 4 carbon atoms.
R _{122 to} R ₁₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{122 to} R ₁₂₅ is many. Represents a cyclic alkyl group. R ₁₂₃ and R ₁₂₄ may be bonded to each other to form a ring.

In the general formulas (p1-I) to (p1-V), the alkyl group in R _{112 to} R ₁₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

The cycloalkyl group in R _{111 to} R ₁₂₅ or the cycloalkyl group formed by Z and the carbon atom is polycyclic. Specific examples include groups having 5 or more carbon atoms such as bicyclo, tricyclo, and tetracyclo structures. The carbon number is preferably 6-30, and particularly preferably 7-25. These polycyclic alkyl groups may further have a substituent.

  Preferred examples of the polycyclic alkyl group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, and a cedrol group. More preferred examples include an adamantyl group, norbornyl group, tetracyclododecanyl group, and tricyclodecanyl group.

  As further substituents for these polycyclic alkyl groups, alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (2 carbon atoms) To 6). Examples of the substituent that the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

The resin (B1) more preferably contains a structure represented by the general formula (p1-I) or (p1-II), and in particular, a polycyclic aliphatic group represented by the general formula (p1-I). Is a 2-adamantyl group or 2-norbornyl group, or the polycyclic aliphatic group represented by the general formula (p1-II) is preferably a 1-adamantyl group.
The structures represented by the general formulas (p1-I) to (p1-V) in the resin can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.

  Specific examples include a structure in which a hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, or a thiol group is substituted with a structure represented by the general formulas (p1-I) to (p1-V). A structure in which a hydrogen atom of a carboxylic acid group or a sulfonic acid group is substituted with a structure represented by general formulas (p1-I) to (p1-V) is preferable.

  As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (p1-I) to (p1-V), a repeating unit represented by the following general formula (p1-A) is preferable.

Here, R ₁ represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. The plurality of R ₁ may be the same or different from each other.
A ₁ is a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group. Represents a combination. A single bond is preferable.
R ₁ p1 represents any group of the above formulas (p1-I) to (p1-V).

  The repeating unit represented by the general formula (P1-A) is most preferably 2-alkyl-2-adamantyl (meth) acrylate, dialkyl (1-adamantyl) methyl (meth) acrylate, 2-alkyl-2-norbornyl. It is a repeating unit of (meth) acrylate.

  Specific examples of the repeating unit represented by the general formula (P1-A) are shown below.

  The alicyclic hydrocarbon-based acid-decomposable resin (B1) having a polycyclic acid-decomposable group of the present invention preferably has a lactone group. As the lactone group, any group can be used as long as it contains a lactone structure, but it is preferably a group containing a 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed to form a spiro structure are preferred. It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-15). Further, a group having a 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). By using a specific lactone structure, line edge roughness, Development defects are improved.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. n ₂ represents an integer of 0 to 2. When n ₂ 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 group having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-13) include a repeating unit represented by the following general formula (AI). it can.

In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group for R _b0 may have include a hydroxyl group and a halogen atom.

Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R _b0 is preferably a hydrogen atom or a methyl group.

A _b is an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. Represents. Preferred is a single bond or a linking group represented by -Ab ₁ -CO _2- .
Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexyl group, an adamantyl group, or a norbornyl group.

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

[3] Resin (B2) containing a repeating unit represented by formula (L-1) or (L-2) and a repeating unit having a monocyclic aliphatic group that decomposes with an acid to generate an alkali-soluble group
The positive photosensitive composition of the present invention, together with the resin (B1), decomposes with an acid to produce an alkali-soluble group, that is, an acid-decomposable repeating unit having a monocyclic aliphatic group, and a general formula (L- A resin containing a repeating unit represented by 1) or (L-2) and having increased solubility in an alkaline developer by the action of an acid (hereinafter referred to as “acid-decomposable resin (B2)” or “resin (B2)” ").

一般式（Ｌ−１）、（Ｌ−２）中、
Ｒ_Ｌ１は水素原子又はアルキル基を示す。
Ｒ_Ｌ４は複数ある場合は各々独立してアルキル基又はシアノ基を示す。
ｎは１以上の整数を表す。
Ｒ_Ｌ２は水素原子又はアルキル基を示す。
ＬＺ２はラクトン環の炭素原子２個とともに環を形成するのに必要な原子団を表す。

In general formulas (L-1) and (L-2),
R _L1 represents a hydrogen atom or an alkyl group.
When there are a plurality of R _{L4 s,} each independently represents an alkyl group or a cyano group.
n represents an integer of 1 or more.
R _L2 represents a hydrogen atom or an alkyl group.
LZ2 represents an atomic group necessary for forming a ring together with two carbon atoms of the lactone ring.

  The resin (B2) contains at least one selected from the group of repeating units having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (p2-I) to general formula (p2-V) It is preferable to be a resin. Among these, a resin containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (p2-I) or general formula (p2-II) is more preferable.

In general formulas (p2-I) to (p2-V),
_R211 represents an alkyl group, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z1 together with the carbon atom to which it is bonded. It represents an atomic group necessary for forming a monocyclic alkyl group.
R _{212 to} R ₂₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms, preferably an alkyl group. However, at least one of R _{212 to} R ₂₁₄ , or any of R ₂₁₅ and R ₂₁₆ represents a monocyclic alkyl group.
R _{217 to} R ₂₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{217 to} R ₂₂₁ is a single atom. Represents a cyclic alkyl group. Further, either R ₂₁₉ or R ₂₂₁ represents a linear or branched alkyl group or monocyclic alkyl group having 1 to 4 carbon atoms.
R _{222 to} R ₂₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group, provided that at least one of R _{222 to} R ₂₂₅ is a single atom. Represents a cyclic alkyl group. R ₂₂₃ and R ₂₂₄ may be bonded to each other to form a ring.

In the general formulas (p2-I) to (p2-V), the alkyl group in R _{212 to} R ₂₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

The cycloalkyl group in R _{211 to} R ₂₂₅ or the cycloalkyl group formed by Z and the carbon atom is monocyclic. Specific examples include cycloalkyl groups having 3 or more carbon atoms. The number of carbon atoms is preferably 4 to 10, and particularly preferably 5 to 8 carbon atoms. These monocyclic alkyl groups may have a substituent.

  Preferred examples of the monocyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group. More preferably, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group can be mentioned.

  As further substituents for these monocyclic alkyl groups, alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (2 carbon atoms). To 6). Examples of the substituent that the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

The resin (B2) preferably contains a monocyclic aliphatic group represented by the general formula (p2-I) or a monocyclic aliphatic group represented by the general formula (p2-II). In addition, the monocyclic aliphatic group represented by the general formula (p2-I) is either a cyclohexyl group or a cyclopentyl group, or the monocyclic aliphatic group represented by the general formula (p2-II) Is more preferably any of a cyclohexyl group, a cyclopentyl group, and a 4-methyl-1-cyclohexyl group.
The structures represented by the general formulas (p2-I) to (p2-V) in the resin can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.

  Specific examples include a structure in which a hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, or a thiol group is substituted with a structure represented by the general formulas (p2-I) to (p2-V). A structure in which a hydrogen atom of a carboxylic acid group or a sulfonic acid group is substituted with a structure represented by general formulas (p2-I) to (p2-V) is preferable.

  As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (p2-I) to (p2-V), a repeating unit represented by the following general formula (p2-A) is preferable.

Here, R ₂ represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R ₂ may be the same or different.
A ₂ is a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, or a single group of two or more groups. Represents a combination. A single bond is preferable.
R ₂ p1 represents any group of the above formulas (p2-I) to (p2-V).

  The repeating unit represented by formula (P2-A) is most preferably 1-alkyl-1-cyclohexyl (meth) acrylate, 1-alkyl-1-cyclopentyl (meth) acrylate, dialkyl (cyclohexyl) methyl (meth) ) A repeating unit of acrylate and dialkyl (cyclopentyl) methyl (meth) acrylate.

  Specific examples of the repeating unit represented by the general formula (P2-A) are shown below.

  The alicyclic hydrocarbon-based acid-decomposable resin (B2) having a monocyclic acid-decomposable group of the present invention has a lactone structure represented by the following general formula (L-1) or (L-2). Has repeating units.

In general formulas (L-1) and (L-2),
R _L1 represents a hydrogen atom or an alkyl group.
When there are a plurality of R _{L4 s,} each independently represents an alkyl group or a cyano group.
n represents an integer of 1 or more.
R _L2 represents a hydrogen atom or an alkyl group.
LZ2 represents an atomic group necessary for forming a ring together with two carbon atoms of the lactone ring.
The ring formed by LZ2 together with two carbon atoms of the lactone ring may be further substituted and may contain a heterocycle.

The alkyl group in R _L1 and R _L2 is preferably a linear alkyl group having 1 to 4 carbon atoms or a perfluoroalkyl group, and the alkyl group in R _L4 is a linear or branched substituted group. Or an alkyl group having 1 to 10 carbon atoms.
The ring formed by LZ2 together with two carbon atoms of the lactone ring may be monocyclic or polycyclic, and the atoms forming the ring may contain heteroatoms such as oxygen atom, sulfur atom and nitrogen atom. The number of atoms forming the ring is preferably 4 to 20 including the atoms of the lactone ring, and the ring may be substituted. The group substituted on the ring is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group, a halogen atom, etc., and a cyclohexyl group having 5 to 10 carbon atoms, for example, in a spiro form. May be substituted.

  Hereinafter, although the example of the repeating unit represented by Formula (L-1) or (L-2) which resin (B2) can contain is shown, this invention is not limited to this.

  The acid-decomposable resins (B1) and (B2) of the present invention may have a repeating unit represented by the following general formula (VIII).

In general formula (VIII):
Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but the present invention is not limited thereto.

  The acid-decomposable resins (B1) and (B2) used in the present invention preferably have a repeating unit having an alkali-soluble group, and more preferably have a repeating unit having a carboxyl group. By having this, the resolution in contact hole applications increases. The repeating unit having a carboxyl group includes a repeating unit in which a carboxyl group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, and a carboxyl group in the main chain of the resin through a linking group. Any of the bonded repeating units is preferable, and the linking group may have a monocyclic or polycyclic hydrocarbon structure. Most preferred are acrylic acid and methacrylic acid.

  The acid-decomposable resins (B1) and (B2) used in the present invention may have a repeating unit having 1 to 3 groups represented by the following general formula (F1). This improves line edge roughness performance.

In general formula (F1), R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group, or an alkoxycarbonyl group).

The alkyl group of R _{50 to} R ₅₅ may be substituted with a halogen atom such as a fluorine atom, a cyano group, etc., preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group or a trifluoromethyl group. be able to.
R _{50 to} R ₅₅ are preferably all fluorine atoms.

  Examples of the organic group represented by Rx include an acid-decomposable protective group and an optionally substituted alkyl group, cycloalkyl group, acyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxycarbonylmethyl group, alkoxymethyl group. , 1-alkoxyethyl group is preferable.

  Preferred examples of the repeating unit having a group represented by the general formula (F1) include a repeating unit represented by the following general formula (F2).

In General Formula (F2), Rx represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rx may have include a hydroxyl group and a halogen atom.
Fa represents a single bond or a linear or branched alkylene group, preferably a single bond.
Fb represents a monocyclic or polycyclic hydrocarbon group.
Fc represents a single bond or a linear or branched alkylene group, preferably a single bond or a methylene group.
F1 represents a group represented by the general formula (F1).
P1 represents 1-3.

  The cyclic hydrocarbon group in Fb is preferably a cyclopentyl group, a cyclohexyl group, or a norbornyl group.

  Specific examples of the repeating unit having the structure of the general formula (F1) are shown below.

  In addition to the above repeating structural units, the acid-decomposable resins (B1) and (B2) of the present invention have the dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics of resist. Various repeating structural units can be included for the purpose of adjusting certain resolution, heat resistance, sensitivity, and the like.

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

  Thereby, the performance required for the acid-decomposable resins (B1) and (B2), in particular, (1) solubility in coating solvents, (2) film-forming properties (glass transition point), (3) alkali developability, Fine adjustments such as (4) film slippage (selection of hydrophilicity / hydrophobicity and alkali-soluble group), (5) adhesion of the unexposed part to the substrate, and (6) dry etching resistance can be made.

  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 acid-decomposable resins (B1) and (B2), the molar ratio of each repeating structural unit depends on resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance. It is appropriately set to adjust a certain resolution, heat resistance, sensitivity, and the like.

  In the acid-decomposable resin (B1), the content of the repeating unit having an acid-decomposable polycyclic aliphatic group is preferably 10 to 60 mol%, more preferably 20 to 50 mol% in all repeating structural units. More preferably, it is 25-40 mol%.

  In the acid-decomposable resin (B2), the content of the repeating unit (L-1) or (L-2) is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, further preferably from all repeating units. Is 30-70 mol%.

  In the acid-decomposable resin (B2), the content of the repeating unit having an acid-decomposable monocyclic aliphatic group is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, more preferably from all repeating units. Preferably it is 30-70 mol%.

When the composition of the present invention is for ArF exposure, the resin preferably has no aromatic group from the viewpoint of transparency to ArF light.
The acid-decomposable resins (B1) and (B2) used in the present invention are preferably those in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units may be methacrylate, all of the repeating units may be acrylate, or a mixture of methacrylate / acrylate, but the acrylate repeating unit is preferably 50 mol% or less of the entire repeating unit.

The acid-decomposable resins (B1) and (B2) used in the present invention 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 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 generally 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50 ° C to 100 ° C.

  When the composition of the present invention is used for the upper resist of the multilayer resist, the acid-decomposable resins (B1) and (B2) preferably have a silicon atom.

As the resin having a silicon atom and decomposing by the action of an acid to increase the solubility in an alkaline developer, a resin having a silicon atom in at least one of a main chain and a side chain can be used. Examples of the resin having a siloxane structure in the side chain of the resin include, for example, an olefin monomer having a silicon atom in the side chain, maleic anhydride and a (meth) acrylic acid monomer having an acid-decomposable group in the side chain. Mention may be made of copolymers.
As the resin having a silicon atom, a resin having a trialkylsilyl structure or a monocyclic or polycyclic siloxane structure is preferable, and a resin having a structure represented by the following general formulas (SS-1) to (SS-4) is used. The resin which has the structure represented by general formula (SS-1)-(SS-4) is more preferable, and the resin which has a (meth) acrylate type repeating unit which has a structure represented by general formula (SS-1)-(SS-4), or an allyl type repeating unit preferable.

  In general formulas (SS-1) to (SS-4), Rs represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group.

  The resin having a silicon atom preferably has a repeating unit having two or more different types of silicon atoms, more preferably (Sa) a repeating unit having 1 to 4 silicon atoms and (Sb) 5 to 10 silicon atoms. A resin having both of the repeating units, and more preferably, at least one repeating unit having a structure represented by formulas (SS-1) to (SS-3) and formula (SS-4). It is resin which has a repeating unit which has the structure represented by these.

When the positive photosensitive composition of the present invention is irradiated with F ₂ excimer laser light, the acid-decomposable resins (B1) and (B2) have fluorine atoms substituted on the main chain and / or side chain of the polymer skeleton. A resin having a structure and being decomposed by the action of an acid to increase the solubility in an alkali developer is preferred, and more preferably a hydroxyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group or a 1-position at a fluorine atom or a fluoro A resin containing a group in which a hydroxyl group substituted with an alkyl group is protected with an acid-decomposable group, and particularly preferably a hexafluoro-2-propanol structure or a structure in which the hydroxyl group of hexafluoro-2-propanol is protected with an acid-decomposable group Resin. By introducing fluorine atoms, it is possible to improve transparency to far ultraviolet light, particularly F ₂ (157 nm) light.

  Preferred examples of the acid-decomposable resins (B1) and (B2) having fluorine atoms include resins having at least one repeating unit represented by the following general formulas (FA) to (FG).

In general formulas (FA) to (FG),
R ₁₀₀ to R ₁₀₃ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an aryl group.
R ₁₀₄ and R ₁₀₆ each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and at least one of R ₁₀₄ and R ₁₀₆ represents a fluorine atom or a fluoroalkyl group. R ₁₀₄ and R ₁₀₆ are preferably both trifluoromethyl groups.
R ₁₀₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or a group capable of decomposing by the action of an acid.
A ₁ is a single bond, a divalent linking group, for example, a linear, branched, cyclic alkylene group, alkenylene group, arylene group, —OCO—, —COO—, or —CON (R ₂₄ ) —, and of these Represents a linking group in which a plurality of these are bonded. R ₂₄ represents a hydrogen atom or an alkyl group.
R ₁₀₇ and R ₁₀₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or a group that decomposes under the action of an acid.
R ₁₀₉ represents a hydrogen atom, an alkyl group, a cycloalkyl group or a group capable of decomposing by the action of an acid.
a is 0 or 1.
b is 0, 1 or 2;
R ₁₀₀ and R ₁₀₁ in the general formulas (FA) and (FC) may form a ring via an alkylene group (having 1 to 5 carbon atoms) which may be substituted with fluorine.

  The repeating units represented by the general formulas (FA) to (FG) contain at least one, preferably three or more fluorine atoms per one repeating unit.

The weight average molecular weights of the acid-decomposable resins (B1) and (B2) are each preferably 2,000 to 200,000 as polystyrene-converted values by the GPC method. By setting the weight average molecular weight to 2,000 or more, heat resistance, dry etching resistance, and exposure latitude can be improved. By setting the weight average molecular weight to 200,000 or less, development defects due to improved developability are achieved. The improvement effect is obtained, and the film forming property can be improved because the viscosity is lowered. The molecular weight is more preferably 5,000 to 50,000, still more preferably 7,000 to 30,000, and most preferably 8000 to 16000.
The dispersity (Mw / Mn) of the acid-decomposable resins (B1) and (B2) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and still more preferably 1 0.0-2.0. The line edge roughness performance can be improved by adjusting the degree of dispersion to an appropriate range.

  The resin (B1) and the resin (B2) may be used alone or as a plurality of resins, but at least one from the group of resins (B1) and at least one from the group of resins (B2) are used. The weight ratio of the resin (B1) group and the resin (B2) group is preferably 1:99 to 99: 1, more preferably 5:95 to 95: 5, and even more preferably 10:90. A range of 90:10 is more preferred.

  In the positive photosensitive composition of the present invention, the blending amount of the acid-decomposable resins (B1) and (B2) according to the present invention in the entire composition is preferably 40 to 99.99% by mass in the total solid content, More preferably, it is 50-99 mass%, More preferably, it is 80-96 mass%.

[4] (C) Solvent The positive photosensitive composition of the present invention is usually used by dissolving each component in a predetermined solvent.
Solvents that can be used include, for example, 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, propyl pyruvate, N, N- Examples thereof include dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran.

  In the present invention, the solvent may be used alone or mixed, but it is preferable to use a mixed solvent containing two or more kinds of solvents having different functional groups. As the mixed solvent having different functional groups, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group are mixed, or a mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed. Is preferably used. As a result, the generation of particles during storage of the photosensitive liquid can be reduced.

  Examples of the solvent having 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. Propylene glycol monomethyl ether and ethyl lactate are more preferable.

  Examples of the solvent having no hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide. Of these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are more preferable, and propylene glycol monomethyl ether acetate, ethyl ethoxypropio Nate, 2-heptanone and cyclohexanone are particularly preferred.

  The mixing ratio (mass) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is usually 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. is there. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.

In a mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed, 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, γ-butyrolactone, and butyl acetate, with propylene glycol monomethyl ether acetate being preferred.
The mixing ratio (mass) of the solvent having an ester structure and the solvent having a ketone structure is usually 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. is there. 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.

[5] (D) Basic compound The positive photosensitive composition of the present invention preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating.

  Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

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 20 carbon atoms or a cycloalkyl group having 3 to 20 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.

  In the positive photosensitive composition of the present invention, the basic compound is used alone or in combination of two or more. The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of a positive photosensitive composition in total, 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.

[6] (E) A dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “component (E)” or “dissolution inhibiting compound”), which is decomposed by the action of an acid to increase the solubility in an alkaline developer.
(E) As a dissolution-inhibiting compound having a molecular weight of 3000 or less that decomposes by the action of an acid and increases its solubility in an alkaline developer, the transmittance of 220 nm or less is not lowered, so Proceeding of SPIE, 2724,355 (1996) An alicyclic or aliphatic compound containing an acid-decomposable group is preferred, such as a cholic acid derivative containing an acid-decomposable group described in 1. Examples of the acid-decomposable group and alicyclic structure are the same as those described above for the alicyclic hydrocarbon-based acid-decomposable resin.

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

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

  The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the solid content of the positive photosensitive composition.

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

[7] (F) Surfactant The positive photosensitive composition of the present invention preferably contains a surfactant, and is a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based interface). It is more preferable to contain any one or two or more of activators and surfactants containing both fluorine atoms and silicon atoms.

  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 photosensitive 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 EFTOP EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 and 4430 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176 and F189. , F113, F110, F177, F120, R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (Manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M , EF135M, EF351, 352, EF801, EF802, EF 01 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204D, 208G, 218G, 230G, 204D, 208D, 212D, 218, 222D (manufactured by Neos) 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.

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

  Surfactants may be used alone or in several combinations.

  The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the positive photosensitive composition (excluding the solvent).

<Other additives>
The positive photosensitive composition of the present invention further promotes solubility in dyes, light absorbers, plasticizers, surfactants other than the component (F), photosensitizers, and developers as necessary. A compound etc. can be contained.

  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.

  The preferable addition amount of these dissolution promoting compounds is 2 to 50% by mass, more preferably 5 to 30% by mass with respect to the resins (B1) and (B2). 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 No. 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.

  As a plasticizer, in addition to a commercially available plasticizer, any compound having a molecular weight of 1000 or less that is compatible with the polymer to be used and has an effect of lowering the softening point of the film may be used without particular limitation. From the viewpoint of compatibility, a molecular weight of 750 or less is preferable, and a molecular weight of 500 or less is more preferable. A compound having a normal pressure boiling point of 300 ° C. or higher and a melting point of 20 ° C. or lower is preferable. Specific examples include diisobutyl phthalate, tricresyl phosphate, triethylene glycol diphenyl ether, diethylene glycol dibenzoate, and triethylene glycol diacetate.

  As the light absorber, any compound that has absorption at the exposure wavelength and does not generate an acid upon exposure can be used without particular limitation. When the light source wavelength is 193 nm, a compound containing an aromatic ring is preferred. Specific examples include benzene derivatives, naphthalene derivatives, anthracene derivatives, furan derivatives, thiophene derivatives, indole derivatives, and the like.

  In the present invention, a surfactant other than the (F) fluorine-based and / or silicon-based surfactant may be added. Specifically, nonionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan aliphatic esters, polyoxyethylene sorbitan aliphatic esters, etc. Mention may be made of activators.

  These surfactants may be added alone or in some combination.

(Pattern formation method)
The positive photosensitive composition of the present invention is used by dissolving the above components in a predetermined solvent, preferably the mixed solvent, and applying the solution on a predetermined support as follows.

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) and developed. Thereby, a good pattern can be obtained.
Exposure (immersion exposure) may be performed by filling a liquid having a higher refractive index than air between the photosensitive film and the lens during irradiation with actinic rays or radiation. Thereby, resolution can be improved.

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. Examples of the alkali developer for the photosensitive composition include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and 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, etc. Alkaline aqueous solutions of 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 further more concretely, this invention is not limited to a following example.
Examples 2 to 4 and 7 are reference examples.
Below, the repeating unit used for the synthesis | combination of resin (B1) and resin (B2) used for the present Example and the comparative example is shown.

Synthesis Example (1) Synthesis of Resin (B1-1) LM-8, PM1-4, IM-1 was charged at a ratio of 40/40/20 (molar ratio) and dissolved in methyl ethyl ketone, and a solid content concentration of 30% 450 g was prepared. To this solution, 10 mol% of V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added and added dropwise to 40 g of methyl ethyl ketone heated to 65 ° C. over 6 hours in a nitrogen atmosphere. The reaction liquid was stirred for 4 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of a mixed solvent of methanol / ISO propyl alcohol = 3/1, and the precipitated white powder was collected, and the obtained powder was reslurried with 1 L of methanol. The target resin (B1-1) was recovered.
The polymer composition ratio determined from NMR was 41/38/21. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 8500, and dispersion degree Mw / Mn = 1.8.
Thereafter, resins (B1-2) to (B1-20) and (B2-1) to (B2-20) were synthesized in the same manner. Table 1 summarizes the monomer types used, the composition ratio obtained from NMR of the obtained resin, the weight average molecular weight obtained by GPC measurement, and the degree of dispersion.

  The structure of the synthesized resin is shown below.

(Examples 1-8, Comparative Examples 1-12)
The total amount of the resins shown in Table 1 synthesized in the above synthesis examples in the proportions shown in Table 2 is 2 g, the photoacid generator 0.2 mmol, the organic basic compound (amine) 10 mg, and the surfactant (2 mg) in Table 2. It mix | blends as shown, and it melt | dissolves in the solvent shown in Table 2 in the ratio of 5.5 weight% of solid content, respectively, Then, it filters with a 0.1 micrometer micro filter, Examples 1-8 and Comparative Examples 1-6. A positive resist composition was prepared.

(Evaluation test)
First, ARC29A manufactured by Brewer Science was applied onto a silicon wafer using a spin coater and heated on a hot plate at 205 ° C. for 60 seconds to form a coating film of ARC29A with a film thickness of 78 nm. The obtained positive resist composition solution is applied thereon and heated on a hot plate at 120 ° C. for 60 seconds to form a positive photoresist film of about 160 nm, which has an L / S pattern of 90 nm. It exposed with the ArF excimer laser (PAS5500 / 1100 by ASML of wavelength 193nm, NA = 0.75) through the 0.6% halftone mask. The heat treatment after exposure was performed at 120 ° C. for 60 seconds, developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds, and rinsed with distilled water to obtain a resist pattern profile.

  The resist pattern of the silicon wafer thus obtained was observed with a scanning microscope (S9260, manufactured by Hitachi, Ltd.), and the resist pattern was obtained with an exposure amount that reproduces a 90 nm (line / space = 1/1) line pattern on the mask. In the range of the edge of 2 μm in the longitudinal direction of the 90 nm line pattern, the distance from the reference line where the edge should be was measured at 50 points, the standard deviation was obtained, and 3σ was calculated (LWR). A smaller value indicates better performance. The results are shown in Table 2. Each abbreviation in the table is also shown below.

[Basic compounds]
N-1: N, N-dibutylaniline N-2: 2-phenylbenzimidazole N-3: N, N-dihydroxyethylaniline N-4: 2,4,5-triphenylimidazole N-5: 2,6 -Diisopropylaniline N-6: Hydroxyantipyrine N-7: Trismethoxymethoxyethylamine N-8: Triethanolamine

[Surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.)
(Fluorine and silicon)
W-3: 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: KH-20 (Asahi Kasei Corporation)
W-6: PF6320 (made by OMNOVA)

〔solvent〕
SL-1: Propylene glycol monomethyl ether acetate SL-2: Propylene glycol monomethyl ether propionate SL-3: 2-heptanone SL-4: Ethyl lactate SL-5: Propylene glycol monomethyl ether SL-6: Cyclohexanone SL-7: Propylene carbonate

  From Table 2, it is clear that the positive resist composition of the present invention has good LWR.

Claims (10)

(A) a compound that generates an acid upon irradiation with an actinic ray or radiation,
(B1) a resin containing a repeating unit having a polycyclic aliphatic group that decomposes with an acid to generate an alkali-soluble group, and
(B2) A monocyclic aliphatic represented by the repeating unit represented by the following general formula (L-1) or (L-2) and the general formula (p2-I) that decomposes with an acid to generate an alkali-soluble group A positive photosensitive composition comprising a resin containing a repeating unit having a group.

In general formula (p2-I),
R ₂₁₁ represents an alkyl group,
Z2 represents an atomic group necessary for forming a monocyclic alkyl group together with a carbon atom.

In general formulas (L-1) and (L-2),
R _L1 represents a hydrogen atom or an alkyl group.
When there are a plurality of R _{L4 s,} each independently represents an alkyl group or a cyano group.
n represents an integer of 1 or more.
R _L2 represents a hydrogen atom or an alkyl group.
LZ2 represents an atomic group necessary for forming a ring together with two carbon atoms of the lactone ring. The positive photosensitive composition according to claim 1, wherein the polycyclic aliphatic group is represented by the general formula (p1-I) or (p1-II).

In general formula (p1-I),
R ₁₁₁ represents an alkyl group,
Z1 represents an atomic group necessary for forming a polycyclic alkyl group together with a carbon atom.
In general formula (p1-II),
R ₁₁₂ and R ₁₁₃ each independently represents an alkyl group.
R ₁₁₄ represents a polycyclic alkyl group. The positive photosensitive composition according to claim 2, wherein the polycyclic aliphatic group is represented by the general formula (p1-I). Polycyclic alkyl group is 2-adamantyl group Z1 in the general formula (p1-I) is formed together with a carbon atom, or either of the 2-norbornyl radical, or, as _{R 114} in formula (p1-II) The positive photosensitive composition according to claim 2 , wherein the polycyclic alkyl group is a 1-adamantyl group. A monocyclic alkyl group a cyclohexyl group, wherein Z2 in the general formula (p2-I) is formed together with the carbon atom, to any one of claims 1 to 4, wherein the one der Turkey cyclopentyl group The positive photosensitive composition as described.   The positive photosensitive composition according to any one of claims 1 to 5, wherein the repeating unit having a monocyclic aliphatic group is represented by the following general formula 7.

  In general formula 7,
  Rx is CH ₃ , CF ₃ Or CH ₂ Represents OH.
  Rxa represents an alkyl group having 1 to 4 carbon atoms.   The positive photosensitive composition according to any one of claims 1 to 6, wherein the resin (B1) has a lactone group.   The positive photosensitive composition according to claim 7, wherein the lactone group is represented by the following general formula LC1-4.

In general formula LC1-4,
  Rb ₂ Represents an alkyl group having 1 to 8 carbon atoms or a cyano group.
  n ₂ Represents an integer of 0-2.
  n ₂ When R is 2 or more, there are multiple Rb ₂ May be the same or different, and a plurality of Rb ₂ They may combine to form a ring.   The photosensitive film | membrane formed with the positive photosensitive composition of any one of Claims 1-8. The pattern formation method characterized by including the process of exposing and developing the photosensitive film | membrane of Claim 9 .