JP2011079764A - Cyclic compound, process for producing the same, radiation-sensitive composition and resist pattern-forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyclic compound which has high solubility in a safe solvent and high sensitivity and can obtain a resist pattern having a good shape, a process for producing the same, a radiation-sensitive composition including the same, and a resist pattern-forming method using the radiation-sensitive composition. <P>SOLUTION: The cyclic compound has a specific structure and the radiation-sensitive composition includes the compound, and the resist pattern-forming method uses the composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a cyclic compound represented by a specific chemical structural formula, useful as an acid amplification type non-polymeric resist material, a radiation-sensitive composition containing the same, and a resist pattern forming method using the composition.

Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, a resist thin film prepared by applying a solution of a polymer resist material such as polymethyl methacrylate, polyhydroxystyrene having an acid-dissociable reactive group or polyalkyl methacrylate on a substrate, ultraviolet rays, far ultraviolet rays, electron beams, extreme A line pattern of about 45 to 100 nm is formed by irradiating with ultraviolet rays (EUV), X-rays or the like.
However, since the polymer resist has a large molecular weight of about 10,000 to 100,000 and a wide molecular weight distribution, the lithography using the polymer resist causes roughness on the surface of the fine pattern, making it difficult to control the pattern dimensions. , Yield decreases. Therefore, there is a limit to miniaturization in conventional lithography using a polymer resist material. In order to produce finer patterns, various low molecular weight resist materials have been disclosed.
For example, an alkali developing negative radiation-sensitive composition (see Patent Document 1 and Patent Document 2) using a low molecular weight polynuclear polyphenol compound as a main component has been proposed. There is a drawback that the shape of the resist pattern to be obtained becomes worse.
As a candidate for a low molecular weight resist material, an alkali developing negative radiation-sensitive composition (see Patent Document 3 and Non-Patent Document 1) using a low molecular weight cyclic polyphenol compound as a main component has been proposed.
Since these low molecular weight cyclic polyphenol compounds have a low molecular weight, it is expected to provide a resist pattern having a small molecular size, high resolution, and low roughness. Further, the low molecular weight cyclic polyphenol compound has a rigid cyclic structure in its skeleton, and thus provides high heat resistance despite its low molecular weight.
However, currently disclosed low molecular weight cyclic polyphenol compounds have problems such as low solubility in safe solvents used in semiconductor manufacturing processes, low sensitivity, and poor resist pattern shape. Improvements in compounds are desired.

JP 2005-326838 A JP 2008-145539 A JP 2009-173623 A

T.A. Nakayama, M .; Nomura, K .; Haga, M .; Ueda: Bull. Chem. Soc. Jpn. 71, 2979 (1998)

  An object of the present invention is to provide a cyclic compound having high solubility in a safe solvent, high sensitivity, and good resist pattern shape, a method for producing the same, a radiation-sensitive composition containing the same, and the radiation-sensitive composition It is an object of the present invention to provide a method of forming a resist pattern using

（１）
（式（１）中、Ｌは、独立して、単結合、炭素数１〜２０の直鎖状もしくは分岐状のアルキレン基、炭素数３〜２０のシクロアルキレン基、炭素数６〜２４のアリーレン基、−Ｏ−、−ＯＣ（＝Ｏ）−、−ＯＣ（＝Ｏ）Ｏ−、−Ｎ（Ｒ^５）−Ｃ（＝Ｏ）−、−Ｎ（Ｒ^５）−Ｃ（＝Ｏ）Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−およびこれらの任意の組み合わせからなる群から選択される二価の有機基であり、Ｒ^１は独立して、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシル基、シアノ基、ニトロ基、水酸基、複素環基、ハロゲン、カルボキシル基、炭素数２〜２０のアシル基、炭素数１〜２０のアルキルシリル基、これらの誘導体からなる群から選択される官能基、または水素原子である。但し、その少なくともひとつのＲ^１は水素原子である。Ｒ’は独立して、下記式（１−２）

（１−２）
で表される基であり、Ｒ^２、Ｒ^３は水素原子、炭素数１〜５のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン、カルボキシル基、水酸基、炭素数１〜２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基であり、Ｒ^４は、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン、カルボキシル基、水酸基、炭素数１〜２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基であり、ｐは１〜５の整数であり、ｑは１〜５の整数である。）
２． 下記式（２）で示される第１項記載の環状化合物。

（２）
（式（２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｐ、ｑ、ｍは、前記と同様である。Ｘ_２は水素又はハロゲン原子であり、ｍ_５は０〜３の整数であり、ｍ＋ｍ_５＝４である。）
３． Ｒ’が独立して下記式（１−３）で表される基である第１項記載の環状化合物。Ｒ’は独立して

（１−３）
（式（１−３）中、Ｒ^２、Ｒ^３は水素原子、炭素数１〜５のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン、カルボキシル基、水酸基、および炭素数１〜２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基であり、Ｒ^４は、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン、カルボキシル基、水酸基、炭素数１〜２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基であり、ｐは１〜５の整数である。）
４． カルボニル化合物（Ａ１）からなる群より選ばれる１種以上，およびフェノール性化合物（Ａ２）からなる群より選ばれる１種以上との縮合反応によることを特徴とする、前記式（１）で示される環状化合物の製造方法。
５． 第１項記載の環状化合物および溶媒を含む感放射線性組成物。
６． 前記環状化合物が、炭素数が２〜５９であり１〜４個のホルミル基を有する化合物（アルデヒド性化合物（Ａ１Ａ））と、炭素数６〜１５であり１〜３個のフェノール性水酸基を有する化合物（フェノール性化合物（Ａ２））との縮合反応により合成した、分子量が７００〜５０００の環状化合物（Ａ）の環状化合物である、第５項記載の感放射線性組成物。
７． 固形成分１〜８０重量％および溶媒２０〜９９重量％からなる第５項記載の感放射線性組成物。
８． さらに、可視光線、紫外線、エキシマレーザー、電子線、極端紫外線（ＥＵＶ）、Ｘ線、およびイオンビームからなる群から選ばれるいずれかの放射線の照射により直接的又は間接的に酸を発生する酸発生剤（Ｃ）を含む第５項記載の感放射線性組成物。
９． さらに、酸架橋剤（Ｇ）を含む第５項記載の感放射線性組成物。
１０． さらに、酸拡散制御剤（Ｅ）を含む請求項５記載の感放射線性組成物。
１１． 前記環状化合物が、下記式（２−２）で示される環状化合物である第５項〜第１０項のいずれかに記載の感放射線性組成物。

（２−２）
（式（２−２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｘ_２、ｐ、ｑ、ｍ、ｍ_５は前記と同様である。）
１２． 前記環状化合物が、下記式（３）で示される各化合物からなる群から選ばれる環状化合物である第１１項記載の感放射線性組成物。

（３）
（式（３）中、Ｒ^２、Ｒ^３、Ｒ^４、ｐ、ｑは、前記と同様である。）
１３． 前記固形成分が、環状化合物／酸発生剤（Ｃ）／酸架橋剤（Ｇ）／酸拡散制御剤（Ｅ）／任意成分（Ｆ））を、固形成分基準の重量％で、５０〜９９．９９９／０．００１〜５０／０．５〜５０／０．０１〜５０／０〜５０含有する第７項記載の感放射線性組成物。
１４． スピンコートによりアモルファス膜を形成することができる第５項記載の感放射線性組成物。
１５． 前記アモルファス膜の、２３℃における２．３８重量％テトラメチルアンモニウムヒドロキシド水溶液に対する溶解速度が１０Å／ｓｅｃ以上である第１４項記載の感放射線性組成物。
１６． 前記アモルファス膜にＫｒＦエキシマレーザー、極端紫外線、電子線またはＸ線を照射したもの、又はこれを２０〜２５０℃で加熱した後のアモルファス膜の２．３８重量％テトラメチルアンモニウムヒドロキシド水溶液に対する溶解速度が５Å／ｓｅｃ以下である第１４項記載の感放射線性組成物。
１７． 第５項〜第１６項のいずれかに記載の感放射線性組成物を用いて、基板上にレジスト膜を形成する工程、前記レジスト膜を露光する工程、および前記レジスト膜を現像してレジストパターンを形成する工程を含むレジストパターン形成方法。
１８． 下記式（４）で表されるカルボニル化合物（Ａ１）。

（４）
（式（４）中、Ｒ^２、Ｒ^３、Ｒ^４、ｐ、ｑは、前記と同様である。） As a result of intensive investigations to solve the above problems, the present inventors have found that a cyclic compound having a specific structure has high solubility in a safe solvent, is highly sensitive, and gives a good resist pattern shape. Arrived.
That is, the present invention is as follows.
1. The cyclic compound shown by following formula (1).

(1)
(In the formula (1), L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms. Group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ⁵ ) —C (═O) —, —N (R ⁵ ) —C (═O) O A divalent organic group selected from the group consisting of —, —S—, —SO—, —SO ₂ — and any combination thereof, and R ¹ is independently an alkyl group having 1 to 20 carbon atoms. , A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, and 2 to 2 carbon atoms. Selected from the group consisting of 20 acyl groups, C1-C20 alkylsilyl groups, and derivatives thereof A functional group or a hydrogen atom, provided that at least one R ¹ is a hydrogen atom, and R ′ is independently a group represented by the following formula (1-2):

(1-2)
R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. A functional group selected from the group consisting of an alkoxy group, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, a hydroxyl group, an alkylsilyl group having 1 to 20 carbon atoms, and derivatives thereof, R ⁴ is , An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a heterocyclic group, a halogen, A functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an alkylsilyl group having 1 to 20 carbon atoms, and derivatives thereof, p is an integer of 1 to 5, and q is an integer of 1 to 5. . )
2. The cyclic compound according to item 1, represented by the following formula (2).

(2)
(In the formula (2), R ¹ , R ² , R ³ , R ⁴ , p, q and m are the same as described above. X ₂ is hydrogen or a halogen atom, and m ₅ is an integer of 0 to 3. And m + m ₅ = 4.)
3. The cyclic compound according to claim 1, wherein R ′ is independently a group represented by the following formula (1-3). R 'is independent

(1-3)
(In the formula ^{(1-3), R 2, R} 3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 1 to carbon atoms A functional group selected from the group consisting of 20 alkoxy groups, cyano groups, nitro groups, heterocyclic groups, halogens, carboxyl groups, hydroxyl groups, and alkylsilyl groups having 1 to 20 carbon atoms, and derivatives thereof; ⁴ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a heterocyclic group, (This is a functional group selected from the group consisting of halogen, carboxyl group, hydroxyl group, alkylsilyl group having 1 to 20 carbon atoms, and derivatives thereof, and p is an integer of 1 to 5.)
4). It is represented by the above formula (1), characterized by a condensation reaction with one or more selected from the group consisting of carbonyl compounds (A1) and one or more selected from the group consisting of phenolic compounds (A2). A method for producing a cyclic compound.
5). A radiation-sensitive composition comprising the cyclic compound according to item 1 and a solvent.
6). The cyclic compound has 2 to 59 carbon atoms and 1 to 4 formyl groups (aldehyde compound (A1A)), and 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups. 6. The radiation-sensitive composition according to item 5, which is a cyclic compound of a cyclic compound (A) having a molecular weight of 700 to 5000, synthesized by a condensation reaction with a compound (phenolic compound (A2)).
7). The radiation-sensitive composition according to claim 5, comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent.
8). Furthermore, acid generation that directly or indirectly generates an acid upon irradiation with radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The radiation sensitive composition of Claim 5 containing an agent (C).
9. Furthermore, the radiation sensitive composition of Claim 5 containing an acid crosslinking agent (G).
10. Furthermore, the radiation sensitive composition of Claim 5 containing an acid diffusion control agent (E).
11. The radiation-sensitive composition according to any one of items 5 to 10, wherein the cyclic compound is a cyclic compound represented by the following formula (2-2).

(2-2)
(In formula (2-2), R ² , R ³ , R ⁴ , X ₂ , p, q, m, and m ₅ are the same as described above.)
12 The radiation-sensitive composition according to item 11, wherein the cyclic compound is a cyclic compound selected from the group consisting of compounds represented by the following formula (3).

(3)
(In the formula (3), R ² , R ³ , R ⁴ , p and q are the same as described above.)
13. The solid component is cyclic compound / acid generator (C) / acid cross-linking agent (G) / acid diffusion controller (E) / optional component (F)) in a weight percentage based on the solid component of 50 to 99.99. The radiation-sensitive composition according to item 7, which contains 999 / 0.001 to 50 / 0.5 to 50 / 0.01 to 50/0 to 50.
14 6. A radiation sensitive composition according to item 5, wherein an amorphous film can be formed by spin coating.
15. The radiation-sensitive composition according to claim 14, wherein the dissolution rate of the amorphous film in an aqueous 2.38 wt% tetramethylammonium hydroxide solution at 23 ° C is 10 Å / sec or more.
16. Dissolution rate of the amorphous film irradiated with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or heated at 20 to 250 ° C. in 2.38 wt% tetramethylammonium hydroxide aqueous solution 15. The radiation-sensitive composition according to item 14, wherein the composition is 5 kg / sec or less.
17. A step of forming a resist film on a substrate, a step of exposing the resist film using the radiation-sensitive composition according to any one of Items 5 to 16, and developing the resist film to develop a resist pattern A resist pattern forming method including a step of forming a film.
18. A carbonyl compound (A1) represented by the following formula (4).

(4)
(In the formula (4), R ² , R ³ , R ⁴ , p and q are the same as described above.)

  INDUSTRIAL APPLICABILITY According to the present invention, a cyclic compound having high solubility in a safe solvent, high sensitivity, and good resist pattern shape, a method for producing the same, a radiation-sensitive composition containing the same, and the radiation-sensitive composition are used. A resist pattern forming method can be provided.

Hereinafter, the present invention will be described in detail.
[Cyclic compound and method for producing the same]
The present invention relates to a cyclic compound useful as a resist material and a method for producing the same.

（１）
（式（１）中、Ｌは、独立して、単結合、炭素数１〜２０の直鎖状もしくは分岐状のアルキレン基、炭素数３〜２０のシクロアルキレン基、炭素数６〜２４のアリーレン基、−Ｏ−、−ＯＣ（＝Ｏ）−、−ＯＣ（＝Ｏ）Ｏ−、−Ｎ（Ｒ^５）−Ｃ（＝Ｏ）−、−Ｎ（Ｒ^５）−Ｃ（＝Ｏ）Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−およびこれらの任意の組み合わせからなる群から選択される二価の有機基であり、Ｒ^１は独立して、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシル基、シアノ基、ニトロ基、水酸基、複素環基、ハロゲン、カルボキシル基、炭素数２〜２０のアシル基、炭素数１〜２０のアルキルシリル基、これらの誘導体からなる群から選択される官能基、または水素原子である。但し、その少なくともひとつのＲ^１は水素原子である。Ｒ’は独立して、下記式（１−２）

（１−２）
で表される基であり、Ｒ^２、Ｒ^３は水素原子、炭素数１〜５のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン、カルボキシル基、水酸基、炭素数１〜２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基であり、Ｒ^４は、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン、カルボキシル基、水酸基、炭素数１〜２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基であり、ｐは１〜５の整数であり、ｑは１〜５の整数である。） The cyclic compound of the present invention is a cyclic compound represented by the following formula (1).

(1)
(In the formula (1), L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms. Group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ⁵ ) —C (═O) —, —N (R ⁵ ) —C (═O) O A divalent organic group selected from the group consisting of —, —S—, —SO—, —SO ₂ — and any combination thereof, and R ¹ is independently an alkyl group having 1 to 20 carbon atoms. , A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, and 2 to 2 carbon atoms. Selected from the group consisting of 20 acyl groups, C1-C20 alkylsilyl groups, and derivatives thereof A functional group or a hydrogen atom, provided that at least one R ¹ is a hydrogen atom, and R ′ is independently a group represented by the following formula (1-2):

(1-2)
R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. A functional group selected from the group consisting of an alkoxy group, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, a hydroxyl group, an alkylsilyl group having 1 to 20 carbon atoms, and derivatives thereof, R ⁴ is , An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a heterocyclic group, a halogen, A functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an alkylsilyl group having 1 to 20 carbon atoms, and derivatives thereof, p is an integer of 1 to 5, and q is an integer of 1 to 5. . )

（１−３）
で表される基であることが好ましい。
（式（１−３）中、Ｒ^２、Ｒ^３は水素原子、炭素数１〜５のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン、カルボキシル基、水酸基、炭素数１〜２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基であり、Ｒ^４は、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン、カルボキシル基、水酸基、炭素数１〜２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基であり、ｐは１〜５の整数である。） R ′ independently represents the following formula (1-3)

(1-3)
It is preferable that it is group represented by these.
(In the formula ^{(1-3), R 2, R} 3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 1 to carbon atoms 20 alkoxy group, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, a hydroxyl group, a functional group selected alkylsilyl group having 1 to 20 carbon atoms, and from the group consisting of their derivatives, R ⁴ Are alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, cyano groups, nitro groups, heterocyclic groups, halogens And a functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an alkylsilyl group having 1 to 20 carbon atoms, and derivatives thereof, and p is an integer of 1 to 5.)

The cyclic compound of the present invention has high heat resistance and is amorphous so that it has excellent film-forming properties, no sublimation, excellent alkali developability, etching resistance, and the like. Material).
Also, in terms of production, various aldehydes including industrially produced aromatic aldehydes and phenols such as resorcinol and pyrogallol are used as raw materials to carry out a dehydration condensation reaction with a nonmetallic catalyst such as hydrochloric acid. Since it can be produced in a yield, it is extremely excellent in practicality.

（２）
（式（２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｐ、ｑ、ｍは前記と同様である。Ｘ_２は水素又はハロゲン原子であり、ｍ_５は０〜３の整数であり、ｍ＋ｍ_５＝４である。） The cyclic compound of the present invention is preferably a cyclic compound selected from the group consisting of each compound represented by the following formula (2).

(2)
(In the formula (2), R ¹ , R ² , R ³ , R ⁴ , p, q and m are the same as described above. X ₂ is hydrogen or a halogen atom, and m ₅ is an integer of 0 to 3. Yes, m + m ₅ = 4.)

（２−２）
（式（２−２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｘ_２、ｐ、ｑ、ｍ、ｍ_５は、前記と同様である。） The cyclic compound of the present invention is preferably a cyclic compound selected from the group consisting of each compound represented by the following formula (2-2).

(2-2)
(In formula (2-2), R ² , R ³ , R ⁴ , X ₂ , p, q, m, and m ₅ are the same as described above.)

（３）
（式（３）中、Ｒ^２、Ｒ^３、Ｒ^４、ｐ、ｑは、前記と同様である。） The cyclic compound of the present invention is preferably a cyclic compound selected from the group consisting of each compound represented by the following formula (3).

(3)
(In the formula (3), R ² , R ³ , R ⁴ , p and q are the same as described above.)

（５）
（式（２−２）中、Ｒ^２、Ｒ^３、ｑは、前記と同様である。） The cyclic compound of the present invention is more preferably a cyclic compound selected from the group consisting of each compound represented by the following formula (5).

(5)
(In formula (2-2), R ² , R ³ and q are the same as described above.)

（６）
（式（６）中、Ｒ^２、Ｒ^３は、前記と同様である。） The cyclic compound of the present invention is more preferably a cyclic compound selected from the group consisting of each compound represented by the following formula (6).

(6)
(In Formula (6), R ² and R ³ are the same as described above.)

（７） More preferably, the cyclic compound of the present invention is a cyclic compound represented by the following formula (7).

(7)

  The molecular weight of the cyclic compound of the present invention represented by the above formula (1) is 700 to 5000, preferably 800 to 2000, more preferably 1000 to 2000. Within the above range, the resolution is improved while maintaining the film formability required for the resist.

  The cyclic compound of the present invention can take a cis form and a trans form, but may have any structure or mixture. When used as a resist component of a radiation-sensitive composition, it is preferable to have only a cis- or trans-structure because it is a pure substance compound and the uniformity of the components in the resist film is high. The method for obtaining a cyclic compound having only a cis- or trans-isomer structure should be performed by a known method such as separation by column chromatography or preparative liquid chromatography or optimization of the reaction solvent and reaction temperature during production. Can do.

  The cyclic compound represented by the above formula (1) is one or more selected from the group consisting of a compound having 2 to 59 carbon atoms and having 1 to 4 formyl groups (aldehyde compound (A1A)), and phenol. It is obtained by a condensation reaction with one or more selected from the group consisting of the functional compound (A2).

  More preferably, the cyclic compound represented by the formula (1) is condensed with one or more selected from the group consisting of carbonyl compounds (A1) and one or more selected from the group consisting of phenolic compounds (A2). Obtained by reaction.

  Instead of the carbonyl compound (A1), an acetal compound (A4) of the carbonyl compound (A1) may be used.

（４）
（式（４）中、Ｒ^２、Ｒ^３、Ｒ^４、ｐ、ｑは前記と同様である。）

アルデヒドであり、例えば、３−フェニルプロパナール、４−フェニルブタナール、５−フェニルペンタナール、６−フェニルヘキサナール、７−フェニルヘプタナール、２−メチルー３−フェニルプロパナール、２−メチルー４−フェニルブタナール、２−メチルー５−フェニルペンタナール、２−メチルー６−フェニルヘキサナール、２−メチルー７−フェニルヘプタナール、２−エチルー３−フェニルプロパナール、２−エチルー４−フェニルブタナール、２−エチルー５−フェニルペンタナール、２−エチルー６−フェニルヘキサナール、２−エチルー７−フェニルヘプタナール、２−プロピルー３−フェニルプロパナール、２−プロピルー４−フェニルブタナール、２−プロピルー５−フェニルペンタナール、２−プロピルー６−フェニルヘキサナール、２−プロピルー７−フェニルヘプタナール、２−ブチルー３−フェニルプロパナール、２−ブチルー４−フェニルブタナール、２−ブチルー５−フェニルペンタナール、２−ブチルー６−フェニルヘキサナール、２−ブチルー７−フェニルヘプタナール、２−ペンチルー３−フェニルプロパナール、２−ペンチルー４−フェニルブタナール、２−ペンチルー５−フェニルペンタナール、２−ペンチルー６−フェニルヘキサナール、２−ペンチルー７−フェニルヘプタナール、２，２−ジメチルー３−フェニルプロパナール、２，２−ジメチルー４−フェニルブタナール、２，２−ジメチルー５−フェニルペンタナール、２，２−ジメチルー６−フェニルヘキサナール、２，２−ジメチルー７−フェニルヘプタナール、３−エチルー２−メチルー３−フェニルプロパナール、３−エチルー２−メチルー４−フェニルブタナール、３−エチルー２−メチルー５−フェニルペンタナール、３−エチルー２−メチルー６−フェニルヘキサナール、３−エチルー２−メチルー７−フェニルヘプタナール、２，２−ジエチルー３−フェニルプロパナール、２，２−ジエチルー４−フェニルブタナール、２，２−ジエチルー５−フェニルペンタナール、２，２−ジエチルー６−フェニルヘキサナール、２，２−ジエチルー７−フェニルヘプタナール、３−（４−メチルフェニル）プロパナール、４−（４−メチルフェニル）ブタナール、５−（４−メチルフェニル）ペンタナール、６−（４−メチルフェニル）ヘキサナール、７−（４−メチルフェニル）ヘプタナール、３−（４−エチルフェニル）プロパナール、４−（４−エチルフェニル）ブタナール、５−（４−エチルフェニル）ペンタナール、６−（４−エチルフェニル）ヘキサナール、７−（４−エチルフェニル）ヘプタナール、３−（４−プロピルフェニル）プロパナール、４−（４−プロピルフェニル）ブタナール、５−（４−プロピルフェニル）ペンタナール、６−（４−プロピルフェニル）ヘキサナール、７−（４−プロピルフェニル）ヘプタナール、３−（４−ブチルフェニル）プロパナール、４−（４−ブチルフェニル）ブタナール、５−（４−ブチルフェニル）ペンタナール、６−（４−ブチルフェニル）ヘキサナール、７−（４−ブチルフェニル）ヘプタナール、２−メチルー３−（４−メチルフェニル）プロパナール、２−メチルー４−（４−メチルフェニル）ブタナール、２−メチルー５−（４−メチルフェニル）ペンタナール、２−メチルー６−（４−メチルフェニル）ヘキサナール、２−メチルー７−（４−メチルフェニル）ヘプタナール、２−メチルー３−（４−エチルフェニル）プロパナール、２−メチルー４−（４−エチルフェニル）ブタナール、２−メチルー５−（４−エチルフェニル）ペンタナール、２−メチルー６−（４−エチルフェニル）ヘキサナール、２−メチルー７−（４−エチルフェニル）ヘプタナール、２−メチルー３−（４−プロピルフェニル）プロパナール、２−メチルー４−（４−プロピルフェニル）ブタナール、２−メチルー５−（４−プロピルフェニル）ペンタナール、２−メチルー６−（４−プロピルフェニル）ヘキサナール、２−メチルー７−（４−プロピルフェニル）ヘプタナール、２−メチルー３−（４−ブチルフェニル）プロパナール、２−メチルー４−（４−ブチルフェニル）ブタナール、２−メチルー５−（４−ブチルフェニル）ペンタナール、２−メチルー６−（４−ブチルフェニル）ヘキサナール、２−メチルー７−（４−ブチルフェニル）ヘプタナール、２−メチルー３−（４−ペンチルフェニル）プロパナール、２−メチルー４−（４−ペンチルフェニル）ブタナール、２−メチルー５−（４−ペンチルフェニル）ペンタナール、２−メチルー６−（４−ペンチルフェニル）ヘキサナール、２−メチルー７−（４−ペンチルフェニル）ヘプタナール等が挙げられ、２−メチルー３−（４−ブチルフェニル）プロパナール、２−メチルー４−（４−ブチルフェニル）ブタナール、２−メチルー５−（４−ブチルフェニル）ペンタナール、２−メチルー６−（４−ブチルフェニル）ヘキサナール、２−メチルー７−（４−ブチルフェニル）ヘプタナール、２−メチルー３−（４−ペンチルフェニル）プロパナール、２−メチルー４−（４−ペンチルフェニル）ブタナール、２−メチルー５−（４−ペンチルフェニル）ペンタナール、２−メチルー６−（４−ペンチルフェニル）ヘキサナール、２−メチルー７−（４−ペンチルフェニル）が好ましく、２−メチルー３−（４−ブチルフェニル）プロパナール、２−メチルー４−（４−ブチルフェニル）ブタナール、２−メチルー５−（４−ブチルフェニル）ペンタナール、２−メチルー６−（４−ブチルフェニル）ヘキサナール、２−メチルー７−（４−ブチルフェニル）ヘプタナールがより好ましい。カルボニル化合物（Ａ１）は本発明の効果を損ねない範囲で炭素数１〜４の直鎖または分岐アルキル基、シアノ基、水酸基、ハロゲン等を有していても良い。カルボニル化合物（Ａ１）は、単独で又は二種以上組み合わせて使用してもよい。 The carbonyl compound (A1) is represented by the following formula (4).

(4)
(In the formula (4), R ² , R ³ , R ⁴ , p and q are the same as above.)

Aldehydes such as 3-phenylpropanal, 4-phenylbutanal, 5-phenylpentanal, 6-phenylhexanal, 7-phenylheptanal, 2-methyl-3-phenylpropanal, 2-methyl-4-phenyl Butanal, 2-methyl-5-phenylpentanal, 2-methyl-6-phenylhexanal, 2-methyl-7-phenylheptanal, 2-ethyl-3-phenylpropanal, 2-ethyl-4-phenylbutanal, 2-ethyl- 5-phenylpentanal, 2-ethyl-6-phenylhexanal, 2-ethyl-7-phenylheptanal, 2-propyl-3-phenylpropanal, 2-propyl-4-phenylbutanal, 2-propyl-5-phenylpentanal, 2-propyl-6- Phenylhexanal, 2-propyl-7-phenylheptanal, 2-butyl-3-phenylpropanal, 2-butyl-4-phenylbutanal, 2-butyl-5-phenylpentanal, 2-butyl-6-phenylhexanal, 2-butyl- 7-phenylheptanal, 2-pentyl-3-phenylpropanal, 2-pentyl-4-phenylbutanal, 2-pentyl-5-phenylpentanal, 2-pentyl-6-phenylhexanal, 2-pentyl-7-phenylheptanal, 2,2-dimethyl-3-phenylpropanal, 2,2-dimethyl-4-phenylbutanal, 2,2-dimethyl-5-phenylpentanal, 2,2-dimethyl-6-phenylhexanal, 2,2-dimethyl-7- Phenylheptanal, -Ethyl-2-methyl-3-phenylpropanal, 3-ethyl-2-methyl-4-phenylbutanal, 3-ethyl-2-methyl-5-phenylpentanal, 3-ethyl-2-methyl-6-phenylhexanal, 3-ethyl-2 -Methyl-7-phenylheptanal, 2,2-diethyl-3-phenylpropanal, 2,2-diethyl-4-phenylbutanal, 2,2-diethyl-5-phenylpentanal, 2,2-diethyl-6-phenylhexanal 2,2-diethyl-7-phenylheptanal, 3- (4-methylphenyl) propanal, 4- (4-methylphenyl) butanal, 5- (4-methylphenyl) pentanal, 6- (4-methylphenyl) ) Hexanal, 7- (4-methylphenyl) heptanal, 3- (4-ethylphenyl) propanal, 4- (4-ethylphenyl) butanal, 5- (4-ethylphenyl) pentanal, 6- (4-ethylphenyl) hexanal, 7- (4-ethylphenyl) heptanal, 3 -(4-propylphenyl) propanal, 4- (4-propylphenyl) butanal, 5- (4-propylphenyl) pentanal, 6- (4-propylphenyl) hexanal, 7- (4-propylphenyl) heptanal, 3- (4-butylphenyl) propanal, 4- (4-butylphenyl) butanal, 5- (4-butylphenyl) pentanal, 6- (4-butylphenyl) hexanal, 7- (4-butylphenyl) heptanal 2-methyl-3- (4-methylphenyl) propanal, 2-methyl-4 (4-methylphenyl) butanal, 2-methyl-5- (4-methylphenyl) pentanal, 2-methyl-6- (4-methylphenyl) hexanal, 2-methyl-7- (4-methylphenyl) heptanal, 2-methyl- 3- (4-ethylphenyl) propanal, 2-methyl-4- (4-ethylphenyl) butanal, 2-methyl-5- (4-ethylphenyl) pentanal, 2-methyl-6- (4-ethylphenyl) hexanal, 2-methyl-7- (4-ethylphenyl) heptanal, 2-methyl-3- (4-propylphenyl) propanal, 2-methyl-4- (4-propylphenyl) butanal, 2-methyl-5- (4-propylphenyl) ) Pentanal, 2-methyl-6- (4-propylphenyl) hexanal, 2 Methyl-7- (4-propylphenyl) heptanal, 2-methyl-3- (4-butylphenyl) propanal, 2-methyl-4- (4-butylphenyl) butanal, 2-methyl-5- (4-butylphenyl) pentanal 2-methyl-6- (4-butylphenyl) hexanal, 2-methyl-7- (4-butylphenyl) heptanal, 2-methyl-3- (4-pentylphenyl) propanal, 2-methyl-4- (4-pentyl) Phenyl) butanal, 2-methyl-5- (4-pentylphenyl) pentanal, 2-methyl-6- (4-pentylphenyl) hexanal, 2-methyl-7- (4-pentylphenyl) heptanal, and the like. 3- (4-Butylphenyl) propanal, 2-methyl-4- (4-buty Ruphenyl) butanal, 2-methyl-5- (4-butylphenyl) pentanal, 2-methyl-6- (4-butylphenyl) hexanal, 2-methyl-7- (4-butylphenyl) heptanal, 2-methyl-3- (4 -Pentylphenyl) propanal, 2-methyl-4- (4-pentylphenyl) butanal, 2-methyl-5- (4-pentylphenyl) pentanal, 2-methyl-6- (4-pentylphenyl) hexanal, 2-methyl-7 -(4-pentylphenyl) is preferred, 2-methyl-3- (4-butylphenyl) propanal, 2-methyl-4- (4-butylphenyl) butanal, 2-methyl-5- (4-butylphenyl) pentanal, 2-methyl-6- (4-butylphenyl) hexanal, 2-methyl-7 (4-butylphenyl) heptanal is more preferable. The carbonyl compound (A1) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired. The carbonyl compound (A1) may be used alone or in combination of two or more.

  The carbonyl compound (A1) can be protected with an acetal group, and is stabilized by acetal protection. Acetal protection can be performed by a known method. For example, it can be obtained by reacting with a dihydric alcohol in the presence of an acid.

  Examples of the phenolic compound (A2) include phenol, catechol, resorcinol, hydroquinone, pyrogallol and the like, resorcinol and pyrogallol are preferred, and resorcinol is more preferred. The phenolic compound (A2) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired. You may use a phenolic compound (A2) individually or in combination of 2 or more types.

  The cyclic compound represented by the above formula (1) can be produced by a known method. For example, in an organic solvent such as methanol or ethanol, 0.1 to 10 moles of phenolic compound (A2) and acid catalyst (hydrochloric acid) are used per 1 mole of carbonyl compound (A1) or ethylene acetal compound (A4) of the carbonyl compound. , Sulfuric acid or para-toluenesulfonic acid, etc.), reacted at 60-150 ° C. for about 0.5-20 hours, filtered, washed with alcohol such as methanol, washed with water, filtered, separated and dried To obtain the cyclic compound of the present invention. Instead of the acid catalyst, a basic catalyst (sodium hydroxide, barium hydroxide or 1,8-diazabicyclo [5.4.0] undecene-7 etc.) is used, and the cyclic reaction of the present invention can be carried out by reacting in the same manner. A compound is obtained.

  It is more preferable to use two or more carbonyl compounds (A1) and / or two or more carbonyl compound ethylene acetal compounds (A4) and two or more phenolic compounds (A2). By using two or more carbonyl compounds (A1) and / or two or more carbonyl compound ethylene acetal compounds (A4) and two or more phenolic compounds (A2), the resulting cyclic compound against a semiconductor safety solvent Solubility is improved.

  You may refine | purify as needed in order to reduce the residual metal amount of the cyclic compound of this invention. Further, if the acid catalyst and the cocatalyst remain, generally, the storage stability of the radiation sensitive composition is lowered, or if the basic catalyst remains, generally the sensitivity of the radiation sensitive composition is lowered. The intended purification may be performed. Purification can be performed by a known method as long as the cyclic compound is not denatured, and is not particularly limited. For example, a method of washing with water, a method of washing with an acidic aqueous solution, a method of washing with a basic aqueous solution, or an ion exchange resin. The method of processing, the method of processing by silica gel column chromatography, etc. are mentioned. These purification methods are more preferably performed in combination of two or more. Acidic aqueous solution, basic aqueous solution, ion exchange resin, and silica gel column chromatography should be optimized depending on the metal to be removed, the amount and type of acidic compound and / or basic compound, the type of cyclic compound to be purified, etc. It is possible to select appropriately. For example, as acidic aqueous solution, hydrochloric acid, nitric acid, acetic acid aqueous solution having a concentration of 0.01 to 10 mol / L, aqueous ammonia solution having a concentration of 0.01 to 10 mol / L as basic aqueous solution, cation exchange resin as ion exchange resin, For example, Amberlyst 15J-HG Dry made by Organo can be mentioned. You may dry after refinement | purification. Drying can be performed by a known method, and is not particularly limited. Examples thereof include vacuum drying and hot air drying under conditions where the cyclic compound is not denatured.

  The cyclic compound represented by the above formula (1) can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process.

  The cyclic compound represented by the above formula (1) is useful as a negative resist material that becomes a compound that is hardly soluble in an alkali developer by irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. It is considered that the condensation reaction between the compounds is induced by irradiating the cyclic compound with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, so that the compound becomes insoluble in an alkali developer. The resist pattern thus obtained has a very low LER.

  The cyclic compound of the present invention represented by the above formula (1) can be made into a negative radiation-sensitive composition based on itself as a main component. In addition, the cyclic compound of the present invention is not a main component but an additive for improving sensitivity and etching resistance, for example. Can be added to the radiation sensitive composition. In this case, the cyclic compound is used at 1 to 49.999% by weight of the total weight of the solid component.

  The dissolution rate of the amorphous film of the cyclic compound of the present invention in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C. is preferably 10 Å / sec or more, more preferably 10 to 10,000 Å / sec, and more preferably 100 to 1000 Å. / Sec is more preferable. It can melt | dissolve in an alkali developing solution as it is 10 tons / sec or more, and can be set as a resist. In addition, when the dissolution rate is 10000 kg / sec or less, the resolution may be improved. This is presumed to be due to the increase in the contrast of the interface between the unexposed portion dissolved in the alkali developer and the exposed portion not dissolved in the alkali developer due to the change in solubility of the cyclic compound before and after exposure. Further, there is an effect of reducing LER and reducing defects.

The glass transition temperature of the cyclic compound of the present invention is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. When the glass transition temperature is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape and can provide performance such as high resolution.
The calorific value of crystallization determined by differential scanning calorimetry of the glass transition temperature of the cyclic compound of the present invention is preferably less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the crystallization heat generation amount is less than 20 J / g, or (crystallization temperature) − (glass transition temperature) is within the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.

  In the present invention, the crystallization calorific value, crystallization temperature and glass transition temperature can be determined by measurement and differential scanning calorimetry as follows using DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is put in an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 ml / min). After the rapid cooling, the temperature is again raised to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 ml / min). Further, after rapid cooling, the temperature is increased again to 400 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen gas stream (30 ml / min). The temperature at the midpoint where the discontinuity appears in the baseline (where the specific heat has changed to half) is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature. The calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.

  The cyclic compound of the present invention preferably has a low sublimation property under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower. The low sublimation property means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10%, preferably 5%, more preferably 3%, still more preferably 1%, particularly preferably 0.1. % Or less is preferable. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Moreover, a favorable pattern shape can be given with low LER.

  The cyclic compound of the present invention preferably satisfies F <3.0 (F represents the total number of atoms / (total number of carbon atoms−total number of oxygen atoms)), and more preferably satisfies F <2.5. By satisfying the above conditions, the dry etching resistance is excellent.

  The cyclic compound of the present invention includes propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate, and A solvent selected from ethyl lactate and having the highest solubility for the cyclic compound is preferably at least 1% by weight, more preferably at least 5% by weight, even more preferably at least 10% by weight, particularly at 23 ° C. Preferably, a solvent selected from PGMEA, PGME, and CHN and exhibiting the highest solubility with respect to the cyclic compound is at least 20% by weight at 23 ° C., particularly preferably 20 ° C. with respect to PGMEA at 20 Dissolves by weight% or more. By satisfying the above conditions, the semiconductor manufacturing process can be used in actual production.

  A halogen atom may be introduced into the cyclic compound of the present invention as long as the effects of the present invention are not impaired. The ratio of the number of halogen atoms to the total number of constituent atoms of the cyclic compound is preferably 0.1 to 60%, more preferably 0.1 to 40%, and more preferably 0.1 to 20%. More preferably, it is 0.1 to 10%, Most preferably, it is 1 to 5%. Within the above range, the film formability can be maintained while increasing the sensitivity to radiation. In addition, the solubility in a safe solvent can be improved.

  Nitrogen atoms may be introduced into the cyclic compound of the present invention as long as the effects of the present invention are not impaired. The ratio of the number of nitrogen atoms to the total number of constituent atoms of the cyclic compound is preferably 0.1 to 40%, more preferably 0.1 to 20%, and more preferably 0.1 to 10%. Further preferred is 0.1 to 5%. Within the above range, the line edge roughness of the resulting resist pattern can be reduced. Moreover, as a nitrogen atom, it is preferable that it is a nitrogen atom contained in a secondary amine or a tertiary amine, and it is more preferable that it is a nitrogen atom contained in a tertiary amine.

  As long as the effects of the present invention are not impaired, the cyclic compound of the present invention is irradiated with visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, ion beam irradiation or chemical reaction induced thereby. A crosslinking reactive group that causes a crosslinking reaction may be introduced. The introduction is performed, for example, by reacting a cyclic compound and a crosslinking reactive group introduction reagent in the presence of a base catalyst. Examples of the crosslinking reactive group include a carbon-carbon multiple bond, an epoxy group, an azide group, a halogenated phenyl group, and a chloromethyl group. Examples of the crosslinking reactive group introduction reagent include acids, acid chlorides, acid anhydrides, carboxylic acid derivatives such as dicarbonates and alkyl halides having such a crosslinking reactive group. A radiation-sensitive composition containing a cyclic compound having a crosslinking reactive group is also useful as a non-polymeric radiation-sensitive composition having high resolution, high heat resistance and solvent solubility.

  A non-acid dissociable functional group may be introduced into at least one phenolic hydroxyl group of the cyclic compound of the present invention as long as the effects of the present invention are not impaired. The non-acid-dissociable functional group refers to a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group. For example, C1-20 alkyl group, C3-20 cycloalkyl group, C6-20 aryl group, C1-20 alkoxyl group, cyano group, nitro group, hydroxyl group, Examples thereof include a cyclic group, a halogen, a carboxyl group, a C1-20 alkylsilyl group, and a functional group selected from the group consisting of these derivatives.

  A naphthoquinone diazide ester group may be introduced into at least one phenolic hydroxyl group of the cyclic compound of the present invention as long as the effects of the present invention are not impaired. A compound in which a naphthoquinone diazide ester group is introduced into at least one phenolic hydroxyl group of a cyclic compound can be a negative radiation-sensitive composition based on itself, and a positive radiation-sensitive composition based on itself. It can add to a radiation sensitive composition as an acid generator and an additive.

  As long as the effects of the present invention are not impaired, an acid-generating functional group that generates an acid upon irradiation with radiation may be introduced into at least one phenolic hydroxyl group of the cyclic compound of the present invention. A cyclic polyphenol compound in which an acid-generating functional group that generates an acid upon irradiation with radiation is introduced into at least one phenolic hydroxyl group of the cyclic compound can be used as a negative radiation-sensitive composition based on itself. Can be added to the radiation-sensitive composition as an acid generator or additive.

[Radiation sensitive composition]
The present invention relates to a radiation-sensitive composition containing the cyclic compound represented by the above formula (1) and a solvent.
Further, the present invention is preferably a radiation-sensitive composition comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, and the compound is 50 to 99.999% by weight of the total weight of the solid component. A radiation sensitive composition is preferred.

  The radiation-sensitive composition of the present invention can form an amorphous film by spin coating. The dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present invention in a 2.38 mass% TMAH aqueous solution at 23 ° C is preferably 10 Å / sec or more, more preferably 10 to 10,000 Å / sec, 100 More preferably, it is -1000 kg / sec. It can melt | dissolve in an alkali developing solution as it is 10 tons / sec or more, and can be set as a resist. In addition, when the dissolution rate is 10000 kg / sec or less, the resolution may be improved. This is presumed to be due to the increase in the contrast of the interface between the unexposed portion dissolved in the alkali developer and the exposed portion not dissolved in the alkali developer due to the change in solubility of the cyclic compound before and after exposure. Further, there is an effect of reducing LER and reducing defects.

  2.38 mass% TMAH at 23 ° C. of a portion exposed to radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray of an amorphous film formed by spin-coating the solid component of the radiation-sensitive composition of the present invention. The dissolution rate in the aqueous solution is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, further preferably 0.0005 to 5 Å / sec. If it is 5 Å / sec or less, it is insoluble in an alkali developer and can be used as a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the cyclic compound is dissolved and LER is reduced. There is also an effect of reducing defects.

In the radiation-sensitive composition of the present invention, preferably the solid component is 1 to 80% by weight and the solvent is 20 to 99% by weight, more preferably the solid component is 1 to 50% by weight and the solvent is 50 to 99% by weight, and still more preferably. The solid component is 2 to 40% by weight and the solvent is 60 to 98% by weight, and particularly preferably the solid component is 2 to 10% by weight and the solvent is 90 to 98% by weight.
The amount of the cyclic compound represented by the formula (1) is 50 to 99.999% by weight, preferably 65 to 80% by weight, more preferably 60 to 70% by weight based on the total weight of the solid component. When the blending ratio is as described above, high resolution is obtained and the line edge roughness is reduced.

  The composition of the present invention generates an acid directly or indirectly by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. It is preferable to include one or more acid generators (C). The amount of the acid generator used is the total weight of the solid component (cyclic compound, acid generator (C), acid crosslinking agent (G), acid diffusion controller (E), other components (F), etc.) 0.001 to 50% by weight of the total amount of solid components, the same applies hereinafter), preferably 1 to 40% by weight, more preferably 3 to 30% by weight, and particularly preferably 10 to 25% by weight. By using within the above range, a pattern profile with high sensitivity and low edge roughness can be obtained. In the present invention, the acid generation method is not limited as long as an acid is generated in the system. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing is possible, and if high-energy rays are used, electron beam, extreme ultraviolet rays, X-rays, ion beam, further fine processing Is possible.

（７−１）
（式（７−１）中、Ｒ^１３は、同一でも異なっていても良く、それぞれ独立に、水素原子、直鎖状、分枝状もしくは環状アルキル基、直鎖状、分枝状もしくは環状アルコキシ基、ヒドロキシル基またはハロゲン原子であり；Ｘ^-は、アルキル基、アリール基、ハロゲン置換アルキル基もしくはハロゲン置換アリール基を有するスルホン酸イオンまたはハロゲン化物イオンである。） The acid generator (C) is preferably at least one selected from the group consisting of compounds represented by the following formulas (7-1) to (7-8).

(7-1)
(In formula (7-1), R ¹³ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. group, a hydroxyl group or a halogen atom; X ^- is an alkyl group, an aryl group, a sulfonic acid ion or halide ion having a halogen-substituted alkyl group or halogen-substituted aryl group).

  The compound represented by the formula (7-1) includes triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-. Octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenyl Sulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanes Phonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri ( 4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluene Sulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylben Zensulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6 -Trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate and cyclo (1,3-perfluoropropanedisulfone) at least selected from the group consisting of imidates It is preferable that the type.

（７−２）
（式（７−２）中、Ｒ^１４は、同一でも異なっていても良く、それぞれ独立に、水素原子、直鎖状、分枝状もしくは環状アルキル基、直鎖状、分枝状もしくは環状アルコキシ基、ヒドロキシル基またはハロゲン原子を表す。Ｘ^-は前記と同様である。）

(7-2)
(In formula (7-2), R ¹⁴ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. A group, a hydroxyl group or a halogen atom, X ⁻ is the same as defined above.)

  The compound represented by the formula (7-2) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) Iodonium-2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis ( 4-t Butylphenyl) iodonium hexafluorobenzenesulfonate, bis (4-tert-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, Diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzene Sulfonate, diphenyl Iodonium hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium per From fluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate Preferably, at least one selected from the group consisting of:

（７−３）
（式（７−３）Ｑはアルキレン基、アリーレン基またはアルコキシレン基であり、Ｒ^１５はアルキル基、アリール基、ハロゲン置換アルキル基またはハロゲン置換アリール基である。）

(7-3)
(Formula (7-3) Q is an alkylene group, an arylene group or an alkoxylene group, and R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.)

  The compound represented by the formula (7-3) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( (Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) Succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-Dicarboximide, N- 10-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept It is preferably at least one selected from 5-En 2,3-dicarboximide, and N- (perfluoro--n- C1-12alkyl oxy) group consisting naphthylimide.

（７−４）
（式（７−４）中、Ｒ^１６は、同一でも異なっていても良く、それぞれ独立に、任意に置換された直鎖、分枝もしくは環状アルキル基、任意に置換されたアリール基、任意に置換されたヘテロアリール基または任意に置換されたアラルキル基である。）

(7-4)
(In Formula (7-4), R ¹⁶ may be the same or different, and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.)

The compound represented by the formula (7-4) is diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone. , Di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone, and di (4-trifluoromethylphenyl) disulfone It is preferable.

（７−５）
（式（７−５）中、Ｒ^１７は、同一でも異なっていても良く、それぞれ独立に、任意に置換された直鎖、分枝もしくは環状アルキル基、任意に置換されたアリール基、任意に置換されたヘテロアリール基または任意に置換されたアラルキル基である。）

(7-5)
(In formula (7-5), R ¹⁷ may be the same or different, and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.)

  The compound represented by the formula (7-5) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino). -Phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile And at least one selected from the group consisting of α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

（７−６）
式（７−６）中、Ｒ^１８は、同一でも異なっていても良く、それぞれ独立に、１以上の塩素原子および１以上の臭素原子を有するハロゲン化アルキル基である。ハロゲン化アルキル基の炭素原子数は１〜５が好ましい。

(7-6)
In formula (7-6), R ¹⁸ may be the same or different and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.

（７−７）

(7-7)

（７−８）

(7-8)

In the formulas (7-7) and (7-8), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or cyclopentyl. Group, cycloalkyl group such as cyclohexyl group, alkoxyl group having 1 to 3 carbon atoms such as methoxy group, ethoxy group and propoxy group, or aryl group such as phenyl group, toluyl group and naphthyl group, preferably 6 carbon atoms -10 aryl groups. L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazido-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ¹⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (16-7-1), a carbonyl group, an ester group, an amide group or an ether group. Y ¹⁹ is a hydrogen atom, an alkyl group or an aryl group, and X ²⁰ is independently a group represented by the following formula (16-8-1).

（７−７−１）

(7-7-1)

（７−８−１）
（式（７−８−１）中、Ｚ^２２はそれぞれ独立に、アルキル基、シクロアルキル基またはアリール基であり、Ｒ^２２はアルキル基、シクロアルキル基またはアルコキシル基であり、ｒは０〜３の整数である。）

(7-8-1)
(In formula (7-8-1), Z ²² each independently represents an alkyl group, a cycloalkyl group, or an aryl group, R ²² represents an alkyl group, a cycloalkyl group, or an alkoxyl group, and r is 0 to 3). Is an integer.)

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1, 4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6-bis (phenylsulfonylazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyla) Bissulfonyldiazomethanes such as methylsulfonyl) decane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6 Halogen-containing triazine derivatives such as-(bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) isocyanurate Etc.

Among the acid generators, acid generators having an aromatic ring are preferable, and an acid generator represented by formula (7-1) or (7-2) is more preferable. An acid generator having a sulfonate ion having an aryl group or a halogen-substituted aryl group as X ^{− in the} formula (7-1) or (7-2) is more preferable, and an acid generator having a sulfonate ion having an aryl group Are particularly preferable, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are particularly preferable. LER can be reduced by using the acid generator.
The acid generator (C) can be used alone or in combination of two or more.

  The radiation-sensitive composition of the present invention preferably contains one or more acid crosslinking agents (G). The acid crosslinking agent (G) is a compound that can crosslink the cyclic compound (A) in the molecule or between molecules in the presence of an acid generated from the acid generator (C). Examples of such an acid crosslinking agent (G) include compounds having one or more substituents (hereinafter referred to as “crosslinkable substituents”) having crosslinking reactivity with the cyclic compound (A). it can.

  Specific examples of such crosslinkable substituents include (i) hydroxyalkyl such as hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group), acetoxy (C1-C6 alkyl group) and the like. A group or a substituent derived therefrom; (ii) a carbonyl group such as formyl group, carboxy (C1-C6 alkyl group) or a substituent derived therefrom; (iii) a dimethylaminomethyl group, a diethylaminomethyl group, a di Nitrogen-containing substituents such as methylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group; (iv) glycidyl group-containing substituents such as glycidyl ether group, glycidyl ester group, glycidylamino group; (v) benzyloxy C1-C6 allyloxy (C1-C) such as methyl group, benzoyloxymethyl group 6 alkyl groups), substituents derived from aromatic groups such as C1-C6 aralkyloxy (C1-C6 alkyl groups); (vi) substituents containing polymerizable multiple bonds such as vinyl groups and isopropenyl groups. be able to. As the crosslinkable substituent of the acid crosslinking agent (G) of the present invention, a hydroxyalkyl group, an alkoxyalkyl group, and the like are preferable, and an alkoxymethyl group is particularly preferable.

  Examples of the acid crosslinking agent (G) having a crosslinkable substituent include (i) a methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, a methylol group-containing glycoluril compound, and a methylol group-containing phenol compound. (Ii) alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds, etc. Containing compound; (iii) carboxymethyl group-containing melamine compound, carboxymethyl group-containing benzoguanamine compound, carboxymethyl group-containing urea compound, carboxymethyl group-containing Carboxymethyl group-containing compounds such as recall uril compounds and carboxymethyl group-containing phenol compounds; (iv) bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolak resin epoxy compounds, resole resin epoxy compounds And epoxy compounds such as poly (hydroxystyrene) -based epoxy compounds.

As the acid crosslinking agent (G), it is further possible to use a compound having a phenolic hydroxyl group and a compound and a resin imparted with a crosslinking property by introducing the crosslinking substituent into an acidic functional group in the alkali-soluble resin. it can. The introduction rate of the crosslinkable substituent in that case is usually 5 to 100 mol%, preferably 10 to 60 mol%, more preferably 10 to 60 mol%, based on the total acidic functional groups in the compound having a phenolic hydroxyl group and the alkali-soluble resin. Preferably, it is adjusted to 15 to 40 mol%. Within the above range, the cross-linking reaction occurs sufficiently, and a decrease in the remaining film ratio, a pattern swelling phenomenon, meandering, and the like can be avoided.
In the radiation-sensitive composition of the present invention, the acid crosslinking agent (G) is preferably an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycoluril compound or a resin thereof. Particularly preferred acid crosslinking agents (G) include compounds represented by the following formula (22) and alkoxymethylated melamine compounds (acid crosslinking agents (G1)).

（上記式中、Ｒ^７はそれぞれ独立して、水素原子、アルキル基、またはアシル基を表し；Ｒ^８〜Ｒ^１１はそれぞれ独立して、水素原子、水酸基、アルキル基、またはアルコキシル基を示し；Ｘ^２は、単結合、メチレン基、または酸素原子を示す。）

(In the above formula, each R ⁷ independently represents a hydrogen atom, an alkyl group, or an acyl group; each of R ^{8 to} R ¹¹ independently represents a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxyl group; X ² represents a single bond, a methylene group, or an oxygen atom.)

In Formula (8), R ⁷ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is more preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The acyl group having 2 to 6 carbon atoms is more preferably an acyl group having 2 to 4 carbon atoms, and examples thereof include an acetyl group and a propionyl group. R ^{8 to} R ¹¹ in Formula (8) are preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X ² represents a single bond, a methylene group, or an oxygen atom, and preferably a single bond or a methylene group. R ^{7 to} R ¹¹ and X ² each have a substituent such as an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a hydroxyl group or a halogen atom in addition to the groups exemplified above. You may do it. The plurality of R ⁷ and R ^{8 to} R ¹¹ may be the same or different.

Specific examples of the compound represented by the formula (8-1) include the compounds shown below.

  Specific examples of the compound represented by the formula (8-2) include, for example, N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril. N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) ) Glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, and the like. Among these, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.

Specific examples of the compound represented by the formula (8-3) include the compounds shown below.

Specific examples of the alkoxymethylated melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (ethoxymethyl) melamine N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N, N, N, N, Examples thereof include N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like. Among these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable.
The acid crosslinking agent (G1) is obtained by, for example, condensing a urea compound or a glycoluril compound, and formalin to introduce a methylol group, and then ether with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol. Then, the reaction solution is cooled and the precipitated compound or its resin is recovered. The acid cross-linking agent (G1) can also be obtained as a commercial product such as CYMEL (trade name, manufactured by Mitsui Cyanamid) or Nicalac (manufactured by Sanwa Chemical Co., Ltd.).

  Further, as other particularly preferable acid crosslinking agent (G), the molecule has 1 to 6 benzene rings, and has at least two hydroxyalkyl groups and / or alkoxyalkyl groups in the molecule. And / or a phenol derivative in which an alkoxyalkyl group is bonded to any one of the benzene rings (acid crosslinking agent (G2)). Preferably, the molecular weight is 1500 or less, the molecule has 1 to 6 benzene rings, and the hydroxyalkyl group and / or alkoxyalkyl group has 2 or more in total, and the hydroxyalkyl group and / or alkoxyalkyl group is the benzene. A phenol derivative formed by bonding to any one or a plurality of benzene rings can be given.

  As a hydroxyalkyl group couple | bonded with a benzene ring, C1-C6 things, such as a hydroxymethyl group, 2-hydroxyethyl group, and 2-hydroxy-1-propyl group, are preferable. As an alkoxyalkyl group couple | bonded with a benzene ring, a C2-C6 thing is preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, 2-methoxyethyl And a 2-methoxy-1-propyl group are preferred.

Among these phenol derivatives, particularly preferable ones are listed below.

In the above formula, L ^{1 to} L ⁸ may be the same or different and each independently represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group. A phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. it can. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, they can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.
A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like.

  A phenol derivative having a hydroxymethyl group and / or an alkoxymethyl group synthesized in this manner is preferable in terms of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. preferable. The acid crosslinking agent (G2) may be used alone or in combination of two or more.

Another particularly preferable acid crosslinking agent (G) is a compound having at least one α-hydroxyisopropyl group (acid crosslinking agent (G3)). The structure is not particularly limited as long as it has an α-hydroxyisopropyl group. In addition, the hydrogen atom of the hydroxyl group in the α-hydroxyisopropyl group is one or more acid dissociable groups (R—COO— group, R—SO ₂ — group, etc., R is a straight chain having 1 to 12 carbon atoms) A hydrocarbon group, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a 1-branched alkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms Which represents a substituent selected from the group consisting of: Examples of the compound having the α-hydroxyisopropyl group include one or two kinds such as a substituted or unsubstituted aromatic compound, diphenyl compound, naphthalene compound, and furan compound containing at least one α-hydroxyisopropyl group. The above is mentioned. Specifically, for example, a compound represented by the following general formula (23-1) (hereinafter referred to as “benzene compound (1)”), a compound represented by the following general formula (23-2) (hereinafter referred to as “the benzene compound (1)”). , "Diphenyl compound (2)"), a compound represented by the following general formula (23-3) (hereinafter referred to as "naphthalene compound (3")), and the following general formula (23-4). And the like (hereinafter referred to as “furan compound (4)”).

In the general formulas (9-1) to (9-4), each A ² independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A ² is an α-hydroxyisopropyl group. In general formula (9-1), R ⁵¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkylcarbonyl group having 2 to 6 carbon atoms, or a linear or branched structure having 2 to 6 carbon atoms. The alkoxycarbonyl group of is shown. Furthermore, in general formula (9-2), R ⁵² represents a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —CO—, or —COO—. Moreover, in general formula (9-4), ^R53 and ^R54 show a hydrogen atom or a C1-C6 linear or branched alkyl group mutually independently.

  Specific examples of the benzene compound (1) include α-hydroxyisopropylbenzene, 1,3-bis (α-hydroxyisopropyl) benzene, 1,4-bis (α-hydroxyisopropyl) benzene, and 1,2. , 4-Tris (α-hydroxyisopropyl) benzene, α-hydroxyisopropylbenzenes such as 1,3,5-tris (α-hydroxyisopropyl) benzene; 3-α-hydroxyisopropylphenol, 4-α-hydroxyisopropylphenol , 3,5-bis (α-hydroxyisopropyl) phenol, α-hydroxyisopropylphenols such as 2,4,6-tris (α-hydroxyisopropyl) phenol; 3-α-hydroxyisopropylphenyl methyl ketone, 4-α -Hydroxyisopropyl Nyl methyl ketone, 4-α-hydroxyisopropylphenyl ethyl ketone, 4-α-hydroxyisopropylphenyl n-propyl ketone, 4-α-hydroxyisopropylphenyl isopropyl ketone, 4-α-hydroxyisopropylphenyl n-butyl ketone, 4-α-hydroxyisopropylphenyl · t-butylketone, 4-α-hydroxyisopropylphenyl · n-pentylketone, 3,5-bis (α-hydroxyisopropyl) phenyl · methylketone, 3,5-bis (α-hydroxyisopropyl) ) Α-hydroxyisopropylphenyl alkyl ketones such as phenyl ethyl ketone, 2,4,6-tris (α-hydroxyisopropyl) phenyl methylketone; methyl 3-α-hydroxyisopropylbenzoate , Methyl 4-α-hydroxyisopropyl benzoate, ethyl 4-α-hydroxyisopropyl benzoate, n-propyl 4-α-hydroxyisopropyl benzoate, isopropyl 4-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl benzoate N-butyl acid, t-butyl 4-α-hydroxyisopropylbenzoate, n-pentyl 4-α-hydroxyisopropylbenzoate, methyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3,5-bis ( Alkyl 4-α-hydroxyisopropylbenzoate such as ethyl α-hydroxyisopropyl) benzoate and methyl 2,4,6-tris (α-hydroxyisopropyl) benzoate.

  Specific examples of the diphenyl compound (2) include 3-α-hydroxyisopropylbiphenyl, 4-α-hydroxyisopropylbiphenyl, 3,5-bis (α-hydroxyisopropyl) biphenyl, 3,3 ′. -Bis (α-hydroxyisopropyl) biphenyl, 3,4'-bis (α-hydroxyisopropyl) biphenyl, 4,4'-bis (α-hydroxyisopropyl) biphenyl, 2,4,6-tris (α-hydroxyisopropyl ) Biphenyl, 3,3 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 3,4 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,6, -tetrakis (α-hydroxy) Isopropyl) biphenyl, 2,4,4 ′, 6, -tetrakis (α-hydroxyisopropyl) (Lopyl) biphenyl, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) biphenyl, 2,2 ′, 4 , 4 ′, 6,6′-hexakis (α-hydroxyisopropyl) biphenyl and the like α-hydroxyisopropylbiphenyls; 3-α-hydroxyisopropyldiphenylmethane, 4-α-hydroxyisopropyldiphenylmethane, 1- (4-α-hydroxy) Isopropylphenyl) -2-phenylethane, 1- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 2- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 1- (4-α- Hydroxyisopropylphenyl) -3-phenylpropane, 1- ( -Α-hydroxyisopropylphenyl) -4-phenylbutane, 1- (4-α-hydroxyisopropylphenyl) -5-phenylpentane, 3,5-bis (α-hydroxyisopropyldiphenylmethane, 3,3'-bis (α -Hydroxyisopropyl) diphenylmethane, 3,4'-bis (α-hydroxyisopropyl) diphenylmethane, 4,4'-bis (α-hydroxyisopropyl) diphenylmethane, 1,2-bis (4-α-hydroxyisopropylphenyl) ethane, 1,2-bis (4-α-hydroxypropylphenyl) propane, 2,2-bis (4-α-hydroxypropylphenyl) propane, 1,3-bis (4-α-hydroxypropylphenyl) propane, 2, 4,6-Tris (α-hydroxyisopropyl) dipheny Methane, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) Diphenylmethane, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenylmethane, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,5 ′, 6 Α-hydroxyisopropyldiphenylalkanes such as pentakis (α-hydroxyisopropyl) diphenylmethane, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenylmethane; 3-α-hydroxyisopropyldiphenyl ether 4-alpha-hydroxyisopropyl Diphenyl ether, 3,5-bis (α-hydroxyisopropyl) diphenyl ether, 3,3′-bis (α-hydroxyisopropyl) diphenyl ether, 3,4′-bis (α-hydroxyisopropyl) diphenyl ether, 4,4′-bis ( α-hydroxyisopropyl) diphenyl ether, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ether, 3,4 ′, 5-tris (α-hydroxy) Isopropyl) diphenyl ether, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5,5′- Tetrakis ( -Hydroxyisopropyl) diphenyl ether, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ether, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenyl ether Α-hydroxyisopropyl diphenyl ethers such as 3-α-hydroxyisopropyl diphenyl ketone, 4-α-hydroxyisopropyl diphenyl ketone, 3,5-bis (α-hydroxyisopropyl) diphenyl ketone, 3,3′-bis (α- Hydroxyisopropyl) diphenyl ketone, 3,4'-bis (α-hydroxyisopropyl) diphenyl ketone, 4,4′-bis (α-hydroxyisopropyl) diphenyl ketone, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ketone 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4,6-tetrakis (α-hydroxy) Isopropyl) diphenyl ketone, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4 , 5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ketone, α-hydroxyisopropyl diphenyl ketones such as 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenyl ketone; 3-α-hydroxyisopropylbenzoate phenyl, 4-α-hydroxyisopropylbenzoate Acid phenyl, benzoic acid 3-α-hydroxyisopropylphenyl, benzoic acid 4-α-hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid phenyl, 3-α-hydroxyisopropylbenzoic acid 3-α- Hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoate 4-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoate 3-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoate 4-α-hydroxyisopropyl Phenyl, 3,5-bis (α-hydroxyisopropyl) phenyl benzoate, phenyl 2,4,6-tris (α-hydroxyisopropyl) benzoate, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3-α -Hydroxy Propylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoate 4-α-hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoate 3,5-bis (α-hydroxyisopropyl) phenyl, 4-α-hydroxy Isopropyl benzoate 3,5-bis (α-hydroxyisopropyl) phenyl, benzoate 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoate 3- α-hydroxyisopropylphenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoate 4-α-hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoate 3,5-bis (α- Hydroxyisopropyl) phenyl, 3-α-hydroxyisopro 2,4,6-Tris (α-hydroxyisopropyl) phenyl 4-benzoate, 2,4,6-tris (α-hydroxyisopropyl) phenyl 4-benzoate, 2,4,6-tris (α -Hydroxyisopropyl) benzoic acid 3,5-bis (α-hydroxyisopropyl) phenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4 , 6-tris (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl and the like α-hydroxyisopropylbenzoic acid phenyls and the like.

  Further, specific examples of the naphthalene compound (3) include 1- (α-hydroxyisopropyl) naphthalene, 2- (α-hydroxyisopropyl) naphthalene, 1,3-bis (α-hydroxyisopropyl) naphthalene, 1,4-bis (α-hydroxyisopropyl) naphthalene, 1,5-bis (α-hydroxyisopropyl) naphthalene, 1,6-bis (α-hydroxyisopropyl) naphthalene, 1,7-bis (α-hydroxyisopropyl) Naphthalene, 2,6-bis (α-hydroxyisopropyl) naphthalene, 2,7-bis (α-hydroxyisopropyl) naphthalene, 1,3,5-tris (α-hydroxyisopropyl) naphthalene, 1,3,6-tris (Α-hydroxyisopropyl) naphthalene, 1,3,7-tris (α- Droxyisopropyl) naphthalene, 1,4,6-tris (α-hydroxyisopropyl) naphthalene, 1,4,7-tris (α-hydroxyisopropyl) naphthalene, 1,3,5,7-tetrakis (α-hydroxyisopropyl) ) Naphthalene and the like.

  Specific examples of the furan compound (4) include 3- (α-hydroxyisopropyl) furan, 2-methyl-3- (α-hydroxyisopropyl) furan, 2-methyl-4- (α- Hydroxyisopropyl) furan, 2-ethyl-4- (α-hydroxyisopropyl) furan, 2-n-propyl-4- (α-hydroxyisopropyl) furan, 2-isopropyl-4- (α-hydroxyisopropyl) furan, 2 -N-butyl-4- (α-hydroxyisopropyl) furan, 2-t-butyl-4- (α-hydroxyisopropyl) furan, 2-n-pentyl-4- (α-hydroxyisopropyl) furan, 2,5 -Dimethyl-3- (α-hydroxyisopropyl) furan, 2,5-diethyl-3- (α-hydroxyisopropyl) furan 3,4-bis (α-hydroxyisopropyl) furan, 2,5-dimethyl-3,4-bis (α-hydroxyisopropyl) furan, 2,5-diethyl-3,4-bis (α-hydroxyisopropyl) Examples include francs.

The acid crosslinking agent (G3) is preferably a compound having two or more free α-hydroxyisopropyl groups, the benzene compound (1) having two or more α-hydroxyisopropyl groups, and two or more α-hydroxyisopropyl groups. The diphenyl compound (2) having, and the naphthalene compound (3) having two or more α-hydroxyisopropyl groups are more preferable, α-hydroxyisopropylbiphenyls having two or more α-hydroxyisopropyl groups, α-hydroxy A naphthalene compound (3) having two or more isopropyl groups is particularly preferred.
The acid cross-linking agent (G3) is usually obtained by a method in which an acetyl group-containing compound such as 1,3-diacetylbenzene is reacted with a Grignard reagent such as CH ₃ MgBr to be methylated, and then hydrolyzed. It can be obtained by a method in which an isopropyl group-containing compound such as diisopropylbenzene is oxidized with oxygen or the like to generate a peroxide and then reduced.

  In the present invention, the blending ratio of the acid crosslinking agent (G) is 1 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 2 to 60 parts by weight, per 100 parts by weight of the cyclic compound represented by the formula (1). Particularly preferred is 4 to 40 parts by weight. When the blending ratio of the acid cross-linking agent (G) is 0.5 parts by weight or more, the effect of suppressing the solubility of the resist film in an alkaline developer is improved, the remaining film ratio is decreased, pattern swelling and meandering are caused. Since generation | occurrence | production can be suppressed, it is preferable, and on the other hand, when it is 50 weight part or less, it is preferable from the heat resistance fall as a resist being suppressed.

Further, the blending ratio of at least one compound selected from the acid crosslinking agent (G1), the acid crosslinking agent (G2), and the acid crosslinking agent (G3) in the acid crosslinking agent (G) is not particularly limited. Various ranges can be used depending on the type of substrate used when forming the pattern.
In the total acid crosslinking agent component, the alkoxymethylated melamine compound and / or the compound represented by (9-1) to (9-3) is 50 to 99% by weight, preferably 60 to 99% by weight, more preferably 70%. It is preferable that it is -98 weight%, More preferably, it is 80-97 weight%. Since the resolution can be improved by setting the alkoxymethylated melamine compound and / or the compounds represented by (9-1) to (9-3) to 50% by weight or more of the total acid crosslinking agent component, 99 It is preferable to set the weight% or less because the cross-sectional shape of the pattern is easily a rectangular cross-sectional shape.

In the present invention, an acid diffusion control agent (E) having an action of controlling undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. You may mix | blend with a radiation sensitive composition. By using such an acid diffusion controller (E), the storage stability of the radiation-sensitive composition is improved. Further, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before electron beam irradiation and the holding time after electron beam irradiation can be suppressed, and the process stability is extremely excellent. Examples of such an acid diffusion controller (E) include electron beam radiation decomposable basic compounds such as a nitrogen atom-containing basic compound, a basic sulfonium compound, and a basic iodonium compound. The acid diffusion controller can be used alone or in combination of two or more.
Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that decompose upon exposure. Examples of the nitrogen-containing organic compound include the following general formula (10):

（１０）
で表される化合物（以下、「含窒素化合物（Ｉ）」という。）、同一分子内に窒素原子を２個有するジアミノ化合物（以下、「含窒素化合物（ＩＩ）」という。）、窒素原子を３個以上有するポリアミノ化合物や重合体（以下、「含窒素化合物（ＩＩＩ）」という。）、アミド基含有化合物、ウレア化合物、及び含窒素複素環式化合物等を挙げることができる。尚、上記酸拡散制御剤は、１種単独で用いてもよく、２種以上を併用してもよい。

(10)
(Hereinafter referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (II)”), and a nitrogen atom. Examples thereof include polyamino compounds and polymers having three or more compounds (hereinafter referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. In addition, the said acid diffusion control agent may be used individually by 1 type, and may use 2 or more types together.

In the general formula (24), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with another functional group such as a hydroxyl group. Here, examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group , N-ethylhexyl group, n-nonyl group, n-decyl group and the like. Moreover, as said aryl group, a C6-C12 thing is mentioned, Specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group, etc. are mentioned. Furthermore, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

  Specific examples of the nitrogen-containing compound (I) include mono-cyclohexane such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine and cyclohexylamine. ) Alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine , Methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, dicyclohexylamine and the like di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n- Pentylamine, tri-n-hexylamine, tri-n-heptylamine, -Tri (cyclo) alkylamines such as n-octylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine; Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine , Aromatic amines such as triphenylamine and 1-naphthylamine.

  Specific examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, Tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) ) Propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl)- 2- (4-Hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.

Specific examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.
Specific examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methylpyrrolidone.

  Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri- Examples thereof include n-butylthiourea.

  Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole; pyridine, 2-methylpyridine. 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline And pyridines such as acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2. ] Octane etc. It can gel.

（１１−１）
で表されるスルホニウム化合物、及び下記一般式（１１−２）： Moreover, as a basic compound decomposed | disassembled by the said exposure, the following general formula (11-1):

(11-1)
And the following general formula (11-2):

（１１−２）
で表されるヨードニウム化合物等を挙げることができる。

(11-2)
The iodonium compound etc. which are represented by these can be mentioned.

In the general formulas (11-1) and (11-2), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. -6 alkoxy groups, hydroxyl groups or halogen atoms. Z ⁻ represents HO ⁻ , R—COO ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms, or an alkaryl group having 1 to 6 carbon atoms) or the following general formula. (11-3):

（１１−３）
で表されるアニオンを示す。

(11-3)
An anion represented by

  Specific examples of the basic compound that decomposes upon exposure include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, and diphenyl-4-hydroxyphenyl. Sulfonium acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydro Oxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butylphenyl 4- hydroxyphenyl iodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyl iodonium acetate, include 4-t-butylphenyl-4-hydroxyphenyl iodonium salicylate and the like.

  The amount of the acid diffusion controller (E) is preferably 0.001 to 50% by weight, more preferably 0.001 to 10% by weight, still more preferably 0.001 to 5% by weight, and 0.001 to 3% by weight. % Is particularly preferred. Within the above range, it is possible to prevent degradation in resolution, pattern shape, dimensional fidelity, and the like. Furthermore, even if the holding time from electron beam irradiation to heating after radiation irradiation becomes longer, the shape of the pattern upper layer portion does not deteriorate. Further, when the blending amount is 10% by weight or less, it is possible to prevent a decrease in sensitivity, developability of an unexposed portion, and the like. Further, by using such an acid diffusion control agent, the storage stability of the radiation-sensitive composition is improved, the resolution is improved, and the holding time before irradiation and the holding time after irradiation are reduced. Changes in the line width of the resist pattern due to fluctuations can be suppressed, and the process stability is extremely excellent.

  The radiation-sensitive composition of the present invention includes, as necessary, other components (F) as long as the purpose of the present invention is not impaired, a dissolution accelerator, a dissolution controller, a sensitizer, a surfactant, One or more additives such as organic carboxylic acids or phosphorus oxo acids or derivatives thereof can be added.

[1] Dissolution Accelerator A low molecular weight dissolution accelerator increases the solubility of a cyclic compound during development and moderately increases the dissolution rate of the cyclic compound during development when the solubility of the cyclic compound in an alkali or other developer is too low. It is a component which has an effect | action and can be used in the range which does not impair the effect of this invention. Examples of the dissolution accelerator include low molecular weight phenolic compounds such as bisphenols and tris (hydroxyphenyl) methane. These dissolution promoters can be used alone or in admixture of two or more. Although the compounding quantity of a solubility promoter is suitably adjusted according to the kind of cyclic compound to be used, 0-100 weight part is preferable per 100 weight part of cyclic compounds shown by Formula (1), Preferably 0-30 Parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.

[2] Solubility control agent When the cyclic compound represented by the formula (1) is too soluble in a developing solution such as an alkali, the solubility control agent controls the solubility to moderately increase the dissolution rate during development. It is a component having an action of decreasing. As such a dissolution control agent, those that do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable.
Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. These dissolution control agents can be used alone or in combination of two or more.
The blending amount of the dissolution control agent is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 100 parts by weight, preferably 0 to 30 parts per 100 parts by weight of the cyclic compound represented by the formula (1). Parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.

[3] Sensitizer The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (C), thereby increasing the amount of acid generated. It is a component that improves the apparent sensitivity. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes.
These sensitizers can be used alone or in combination of two or more. Although the compounding quantity of a sensitizer is suitably adjusted according to the kind of cyclic compound to be used, 0-100 weight part is preferable per 100 weight part of cyclic compounds shown by Formula (1), Preferably 0-30 Parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.
[4] Surfactant A surfactant is a component having an action of improving the coating property and striation of the radiation-sensitive composition of the present invention, the developability of a resist, and the like. Such a surfactant may be anionic, cationic, nonionic or amphoteric. A preferred surfactant is a nonionic surfactant. Nonionic surfactants have better affinity with the solvent used in the production of the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers and higher fatty acid diesters of polyethylene glycol, but are not particularly limited. Commercially available products have the following trade names: F-top (manufactured by Gemco), Mega-Fac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass), Examples include Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.)
The blending amount of the surfactant is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 100 parts by weight, preferably 0 to 30 parts per 100 parts by weight of the cyclic compound represented by the formula (1). Parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.

[5] Organic carboxylic acid or phosphorous oxo acid or derivative thereof For the purpose of preventing sensitivity deterioration or improving resist pattern shape, retention stability, etc., organic carboxylic acid or phosphorous oxo acid or derivative thereof as an optional component Can be contained. In addition, it can be used in combination with an acid diffusion controller, or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid such as diphenyl ester phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- Derivatives such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester, etc., phosphonic acid or their esters, phosphinic acid, phosphinic acid such as phenylphosphinic acid, and derivatives thereof Of these, phosphonic acid is particularly preferred.
The organic carboxylic acid or phosphorus oxo acid or derivative thereof may be used alone or in combination of two or more. The amount of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is appropriately adjusted depending on the type of the cyclic compound used, but it is 0 to 100 parts by weight per 100 parts by weight of the cyclic compound represented by the formula (1). Is preferably 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.

[6] The above-mentioned dissolution control agent, sensitizer, surfactant, and other additives other than organic carboxylic acid or phosphorus oxo acid or derivative thereof. One or more additives other than the above-mentioned dissolution control agent, sensitizer, and surfactant can be blended as necessary within a range not inhibiting the purpose. Examples of such additives include dyes, pigments, and adhesion aids. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.

Formulation of the radiation-sensitive composition of the present invention (cyclic compound / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) is weight% based on solids And preferably 50 to 99.999 / 0.001 to 50 / 0.5 to 50 / 0.01 to 50/0 to 50,
More preferably
50 to 99.999 / 0.001 to 50 / 0.5 to 40 / 0.01 to 5/0 to 15,
More preferably, it is 60-70 / 10-25-25 / 1-30 / 0.01-3 / 0-1
Especially preferably, it is 60-70 / 10-25 / 2-20 / 0.01-3 / 0. When the above composition is used, the performance such as sensitivity, resolution and alkali developability is excellent.
When the optional component (F) is not included, the composition of the total solid in the radiation-sensitive composition of the present invention is (A) 3-96.9% by weight, (C) 0.1-30% by weight, ( G) 0.3 to 96.9% by weight, (E) 0.01 to 30% by weight, ((A) + (C) + (G) + (E) = 100% by weight) are preferred, (A) 65-96.9 wt%, (C) 0.1-32 wt%, (G) 0.3-34.9 wt%, (E) 0.01-30 wt%, ((A) + (C ) + (G) + (E) = 100 wt%), (A) 70-96.9 wt%, (C) 0.1-27 wt%, (G) 3.0-29.9 % (E) 0.01-30% by weight, ((A) + (C) + (G) + (E) = 100% by weight) is more preferred, and (A) 80-96.9% by weight, (C) 0.1 to 17% by weight, (G) 3.0 to 9.9% by weight (E) 0.01-30% by weight, ((A) + (C) + (G) + (E) = 100% by weight) is particularly preferred, and (A) 90-96.9% by weight %, (C) 0.1-7 wt%, (G) 3.0-9.9 wt%, (E) 0.01-30 wt%, ((A) + (C) + (G) + (E) = 100% by weight) is most preferred. By setting it within the above range, the performance such as sensitivity, resolution, and alkali developability is excellent.

  The radiation-sensitive composition of the present invention is usually prepared by dissolving each component in a solvent at the time of use to make a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, if necessary. The

  Examples of the solvent used for preparing the radiation-sensitive composition of the present invention include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n- Ethylene glycol monoalkyl ether acetates such as butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n- Propyl ether acetate, propylene glycol mono-n-butyl ether acetate, etc. Lopylene glycol monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; lactic acid such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate Esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyrate Other esters such as acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone Lactones such as γ-lactone can be mentioned, but there is no particular limitation. These solvents can be used alone or in combination of two or more.

  The radiation-sensitive composition of the present invention can contain a resin that is soluble in an alkaline aqueous solution as long as the object of the present invention is not impaired. Resins that are soluble in an alkaline aqueous solution include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and heavy polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units. A combination, or a derivative thereof may be used. The blending amount of the resin that is soluble in the alkaline aqueous solution is appropriately adjusted according to the type of the cyclic compound to be used, but is preferably 30 parts by weight or less, more preferably 10 parts by weight or less per 100 parts by weight of the cyclic compound. More preferably, it is 5 parts by weight or less, particularly preferably 0 part by weight.

[Method of forming resist pattern]
The present invention includes a step of forming a resist film on a substrate using the radiation-sensitive composition of the present invention, a step of exposing the resist film, and a step of developing the resist film to form a resist pattern. The present invention relates to a resist pattern forming method. The resist pattern of the present invention can also be formed as an upper layer resist in a multilayer resist process.
In order to form a resist pattern, a resist film is formed by applying the radiation-sensitive composition of the present invention on a conventionally known substrate by coating means such as spin coating, cast coating, roll coating or the like. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon wafer, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. If necessary, an inorganic and / or organic film may be provided on the substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.
Next, the coated substrate is heated as necessary. Although heating conditions change with the compounding composition etc. of a radiation sensitive composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. Although heating conditions change with the compounding composition of a radiation sensitive resist composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC.

Next, the exposed resist film is developed with an alkaline developer to form a predetermined resist pattern. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution in which one or more compounds are dissolved so as to have a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used. When the concentration of the alkaline aqueous solution is 10% by mass or less, it is preferable because the exposed portion can be prevented from being dissolved in the developer.
In addition, an appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. This is preferable since the wettability of the developer with respect to the resist can be improved. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans with water after image development.

After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.
Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.
The residual resist pattern after etching can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like. As the strong alkaline aqueous solution, for example, 1 to 20% by mass of sodium hydroxide aqueous solution or 1-20 mass% potassium hydroxide aqueous solution is mentioned. Examples of the peeling method include a dipping method and a spray method. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.
The wiring board obtained by the present invention can also be formed by a method of depositing a metal in vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following synthesis examples and examples, the structures of the compounds were confirmed by ¹ H-NMR measurement and LC-MS measurement.

（ＣＲ-１Ａ） Example 1 Synthesis of a cyclic compound
Synthesis of CR-1A A well-dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, four-necked flask (300 mL) equipped with a stirring blade was placed under a nitrogen stream under resorcinol (manufactured by Kanto Chemical Co., Ltd.) 6.15 g, 0.0558 mol), dehydrated ethanol (70 mL) and 8.7 mL of concentrated hydrochloric acid (35%) were added to prepare an ethanol solution. Next, 2-methyl- (4-t-butylphenyl) -3-propanal (10.88 g, 0.0532 mol) manufactured by Tokyo Chemical Industry Co., Ltd. was mixed and added dropwise with a dropping funnel over 10 minutes. It heated to 80 degreeC with the mantle heater, stirring. Subsequently, the mixture was stirred at 80 ° C. for 5 hours. After completion of the reaction, the reaction mixture was allowed to cool to reach room temperature. Concentration under reduced pressure using an evaporator produced a target crude crystal. After the reaction, ethanol was distilled off by evaporation, and 100 mL of distilled water was added. This was filtered off, and the crude crystals were washed 6 times with 100 mL of distilled water, filtered off and dried in vacuo to give the desired product (hereinafter referred to as CR-1A) (16.4 g, yield ˜100%). Got.
As a result of analyzing the structure of this compound by LC-MS, the molecular weight of the target product was 1186. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in deuterated dimethyl sulfoxide solvent is 0.5 to 0.9 (m, 12H), 1.0 to 1.5 (m, 36H), 3 .9 to 4.1 (m, 4H), 6.0 to 6.5 (s, 4H), 6.5 to 7.5 (m, 24H), 8.3 to 10.0 (s, 8H) Met.

(CR-1A)

（ＣＲ−２Ａ） Comparative Example 1
Synthesis of CR-2A A well-dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, four-necked flask (2000 mL) equipped with a stirring blade was placed under a nitrogen stream under resorcinol (manufactured by Kanto Chemical Co., Ltd.) 120 g, 1.09 mol), dehydrated ethanol (1.36 L), and 168 mL of concentrated hydrochloric acid (35%) were added to prepare an ethanol solution. Next, 4-cyclohexylbenzaldehyde (196 g, 1.04 mol) was mixed and added dropwise by a dropping funnel over 10 minutes, and then the solution was heated to 80 ° C. with a mantle heater while stirring. Subsequently, the mixture was stirred at 80 ° C. for 5 hours. After completion of the reaction, the reaction mixture was allowed to cool to reach room temperature. The target crude crystal was formed, and after the reaction, this was filtered off, and 1000 mL of distilled water was added. This was filtered off and the crude crystals were washed 6 times with 1000 mL of distilled water, filtered off and vacuum dried to obtain the desired product (hereinafter referred to as CR-2A) (278 g, 91% yield). .
As a result of analyzing the structure of this compound by LC-MS, it showed the molecular weight 1122 of the target product. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in deuterated dimethyl sulfoxide solvent is 0.8 to 1.9 (m, 44H), 5.5 to 5.6 (d, 4H), 6 0.0 to 6.8 (m, 24H) and 8.4 to 8.5 (m, 8H).

(CR-2A)

Example 2 and Comparative Example 2
(1) Safety solvent solubility test of compound The amount of the compound obtained in Example 1 and Comparative Example 1 dissolved in propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone (CHN) was measured. evaluated. The results are shown in Table 1.
A: 20.0 wt% ≦ dissolved amount B: 3.0 wt% ≦ dissolved amount <20.0 wt%
C: Dissolved amount <3.0 wt%

  The present invention relates to a cyclic compound represented by a specific chemical structural formula, useful as an acid-amplified non-polymer resist material, a radiation-sensitive composition containing the same, and a resist pattern forming method using the radiation-sensitive composition Is preferably used.

Claims (18)

The cyclic compound shown by following formula (1).

(1)
(In the formula (1), L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms. Group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ⁵ ) —C (═O) —, —N (R ⁵ ) —C (═O) O A divalent organic group selected from the group consisting of —, —S—, —SO—, —SO ₂ — and any combination thereof, and R ¹ is independently an alkyl group having 1 to 20 carbon atoms. , A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, and 2 to 2 carbon atoms. An acyl group having 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or a hydrogen atom. In each case, one R ¹ is a hydrogen atom, and R ′ is independently the following formula (1-2):

(1-2)
R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. R ⁴ is a functional group selected from the group consisting of an alkoxy group, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, a hydroxyl group, and an alkylsilyl group having 1 to 20 carbon atoms. -20 alkyl group, cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, cyano group, nitro group, heterocyclic group, halogen, carboxyl group, hydroxyl group , And a functional group selected from the group consisting of alkylsilyl groups having 1 to 20 carbon atoms, p is an integer of 1 to 5, and q is an integer of 1 to 5. ) The cyclic compound of Claim 1 shown by following formula (2).

(2)
(In the formula (2), R ¹ , R ² , R ³ , R ⁴ , p, q and m are the same as described above. X ₂ is hydrogen or a halogen atom, and m ₅ is an integer of 0 to 3. Yes, m + m ₅ = 4.) The cyclic compound according to claim 1, wherein R ′ is independently a group represented by the following formula (1-3).

(1-3)
(In the formula ^{(1-3), R 2, R} 3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 1 to carbon atoms 20 alkoxy group, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, a hydroxyl group, and a functional group selected from the group consisting of alkyl silyl group having a carbon number of 1 to 20, R ⁴ has a carbon number An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, (A functional group selected from the group consisting of a hydroxyl group and an alkylsilyl group having 1 to 20 carbon atoms, and p is an integer of 1 to 5.)   It is represented by the above formula (1), characterized by a condensation reaction with one or more selected from the group consisting of carbonyl compounds (A1) and one or more selected from the group consisting of phenolic compounds (A2). A method for producing a cyclic compound.   A radiation-sensitive composition comprising the cyclic compound according to claim 1 and a solvent.   The cyclic compound has 2 to 59 carbon atoms and 1 to 4 formyl groups (aldehyde compound (A1A)), and 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups. The radiation sensitive composition of Claim 5 which is the cyclic compound of the cyclic compound (A) of molecular weight 700-5000 synthesize | combined by the condensation reaction with a compound (phenolic compound (A2)).   The radiation-sensitive composition according to claim 5, comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent.   Furthermore, acid generation that directly or indirectly generates an acid upon irradiation with radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The radiation sensitive composition of Claim 5 containing an agent (C).   Furthermore, the radiation sensitive composition of Claim 5 containing an acid crosslinking agent (G).   Furthermore, the radiation sensitive composition of Claim 5 containing an acid diffusion control agent (E). The radiation-sensitive composition according to claim 5, wherein the cyclic compound is a cyclic compound represented by the following formula (2-2).

(2-2)
(In formula (2-2), R ² , R ³ , R ⁴ , X ₂ , p, q, m, and m ₅ are the same as described above.) The radiation-sensitive composition according to claim 11, wherein the cyclic compound is a cyclic compound selected from the group consisting of each compound represented by the following formula (3).

(3)
(In the formula (3), R ² , R ³ , R ⁴ , p and q are the same as described above.)   The solid component is cyclic compound / acid generator (C) / acid cross-linking agent (G) / acid diffusion controller (E) / optional component (F)) in a weight percentage based on the solid component of 50 to 99.99. The radiation sensitive composition of Claim 7 containing 999 / 0.001-50 / 0.5-50 / 0.01-50 / 0-50.   The radiation-sensitive composition according to claim 5, wherein an amorphous film can be formed by spin coating.   The radiation-sensitive composition according to claim 14, wherein the dissolution rate of the amorphous film in an aqueous 2.38 wt% tetramethylammonium hydroxide solution at 23 ° C is 10 Å / sec or more.   Dissolution rate of the amorphous film irradiated with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or heated at 20 to 250 ° C. in 2.38 wt% tetramethylammonium hydroxide aqueous solution The radiation-sensitive composition according to claim 14, wherein is 5 Å / sec or less.   A step of forming a resist film on a substrate, a step of exposing the resist film, and a step of developing the resist film to form a resist pattern using the radiation-sensitive composition according to claim 5. A resist pattern forming method including the step of: A carbonyl compound (A1) represented by the following formula (4).

(4)
(In the formula (4), R ² , R ³ , R ⁴ , p and q are the same as described above.)