JP2022130463A - Compound, resin, composition, and resist pattern forming method and circuit pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound, a resin, and a composition that allow the application of a wet process thereto and are useful for forming a photoresist and a photoresist underlayer film having excellent thermostability, solubility and etching resistance.

SOLUTION: The present invention discloses a compound represented by the following formula (where R^Y denotes H; R^Z denotes a C1-60 N-valent group or a single bond; R^T independently denote a substituted/unsubstituted C1-30 alkyl group, a substituted/unsubstituted C6-30 aryl group or the like; where, at least one of R^T is a hydroxy group, and at least one of R^T is a C2-30 alkenyl group; X denotes an oxygen atom, a sulfur atom, a single bond or un-crosslinkage).

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a compound, resin, composition having a specific structure, a resist pattern forming method, and a circuit pattern forming method.

In the manufacture of semiconductor devices, microfabrication is performed by lithography using a photoresist material. However, in recent years, with the increase in the integration density and speed of LSIs, there is a demand for further miniaturization based on pattern rules. In addition, the light source for lithography used in resist pattern formation has been shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm), and extreme ultraviolet light (EUV, 13.5 nm) has been introduced. is also expected.

However, in lithography using conventional polymer-based resist materials, the molecular weight is as large as about 10,000 to 100,000, and the molecular weight distribution is wide, which causes roughness on the pattern surface and makes it difficult to control pattern dimensions, limiting miniaturization. There is Therefore, various low-molecular-weight resist materials have been proposed so far in order to provide resist patterns with higher resolution. Since the low-molecular-weight resist material has a small molecular size, it is expected to provide a resist pattern with high resolution and low roughness.

Currently, various materials are known as such low-molecular-weight resist materials. for example,
An alkali-developable negative radiation-sensitive composition using a low-molecular-weight polynuclear polyphenol compound as a main component (see, for example, Patent Documents 1 and 2) has been proposed, and is a candidate for a low-molecular-weight resist material having high heat resistance. As such, an alkali-developable negative radiation-sensitive composition using a low-molecular-weight cyclic polyphenol compound as a main component (see, for example, Patent Document 3 and Non-Patent Document 1) has also been proposed. In addition, as a base compound of a resist material, a polyphenol compound is known to be capable of imparting high heat resistance while having a low molecular weight, and is useful for improving the resolution and roughness of resist patterns (for example, Non-Patent Document 2). reference).

The present inventors have so far found a resist composition containing a compound with a specific structure and an organic solvent as a material that is excellent in etching resistance, soluble in a solvent, and can be subjected to a wet process (e.g., Patent Document 4 ) is proposed.

In addition, as the resist pattern becomes finer and finer, there arises a problem of resolution or collapse of the resist pattern after development. However, simply thinning the resist makes it difficult to obtain a resist pattern with a film thickness sufficient for substrate processing. Therefore, in addition to the resist pattern, there is a need for a process in which a resist underlayer film is formed between the resist and the semiconductor substrate to be processed, and this resist underlayer film also functions as a mask during substrate processing.

At present, various types of resist underlayer films are known for such processes. For example, unlike conventional resist underlayer films with a high etching rate, terminal groups are removed by applying a predetermined energy to realize a resist underlayer film for lithography that has a dry etching rate selectivity close to that of resist. An underlayer film-forming material for multi-layer resist processes containing a solvent and a resin component having at least a substituent group that is separated to form a sulfonic acid residue has been proposed (see, for example, Patent Document 5). In addition, as a material for realizing a resist underlayer film for lithography having a dry etching rate selectivity ratio smaller than that of a resist,
A resist underlayer film material containing a polymer having a specific repeating unit has been proposed (see, for example, Patent Document 6). Furthermore, in order to realize a resist underlayer film for lithography having a dry etching rate selectivity ratio smaller than that of a semiconductor substrate, acenaphthylene repeating units and repeating units having a substituted or unsubstituted hydroxy group are copolymerized. A resist underlayer film material containing a polymer has been proposed (see, for example, Patent Document 7).

On the other hand, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas, etc. as raw materials is well known as a material having high etching resistance in this type of resist underlayer film. However, from the viewpoint of process, there is a demand for a resist underlayer film material that can form a resist underlayer film by a wet process such as spin coating or screen printing.

In addition, the present inventors have found an underlayer film-forming composition for lithography containing a compound having a specific structure and an organic solvent as a material having excellent etching resistance, high heat resistance, solubility in a solvent, and application of a wet process. proposed a product (see, for example, Patent Document 8).

Furthermore, regarding the method of forming the intermediate layer used in forming the resist underlayer film in the three-layer process, for example, a method of forming a silicon nitride film (see, for example, Patent Document 9) and a method of forming a silicon nitride film by CVD (see, for example, Patent Document 10) is known. Also, 3
Materials containing silsesquioxane-based silicon compounds are known as intermediate layer materials for layer processes (see, for example, US Pat.

Various optical component-forming compositions have also been proposed. For example, acrylic resins (
For example, see Patent Documents 13 and 14) and polyphenols having a specific structure derived from allyl groups (see Patent Document 15, for example) have been proposed.

JP-A-2005-326838 JP 2008-145539 A JP 2009-173623 A WO2013/024778 JP-A-2004-177668 JP 2004-271838 A JP-A-2005-250434 WO2013/024779 JP-A-2002-334869 WO2004/066377 Japanese Patent Application Laid-Open No. 2007-226170 JP 2007-226204 A JP 2010-138393 A JP 2015-174877 A WO2014/123005

T. Nakayama, M.; Nomura, K.; Haga, M.; Ueda: Bull. Chem. Soc. Jpn. , 71, 2979 (1998) Shinji Okazaki, 22 others, "New Development of Photoresist Material Development," CMC Publishing Co., Ltd., September 2009, p. 211-259

As described above, a large number of lithographic film-forming compositions for resist applications and lithographic film-forming compositions for underlayer film applications have been proposed, but wet processes such as spin coating and screen printing are applicable. There is no material that not only has high solvent solubility but also has high heat resistance and etching resistance, and development of a new material is desired.

In addition, although many compositions for optical members have been proposed so far, there is no composition that satisfies both heat resistance, transparency and refractive index at a high level, and the development of new materials is desired.

The present invention has been made in view of the above-mentioned problems of the prior art, and its object is to form a photoresist and an underlayer film for a photoresist that can be applied to a wet process and has excellent heat resistance, solubility and etching resistance. An object of the present invention is to provide compounds, resins, and compositions useful for

（０）
（式（０）中、Ｒ^Yは、水素原子であり、
Ｒ^Zは、炭素数１～６０のＮ価の基又は単結合であり、
Ｒ^Tは、各々独立して、置換基を有していてもよい炭素数１～３０のアルキル基、置換
基を有していてもよい炭素数６～３０のアリール基、置換基を有していてもよい炭素数２
～３０のアルケニル基、置換基を有していてもよい炭素数１～３０のアルコキシ基、ハロ
ゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基又は水酸基であり、前記アル
キル基、前記アリール基、前記アルケニル基及び前記アルコキシ基は、エーテル結合、ケ
トン結合又はエステル結合を含んでいてもよく、ここで、Ｒ^Tの少なくとも１つは水酸基
であり、またＲ^Tの少なくとも１つは炭素数２～３０のアルケニル基であり、
Ｘは、酸素原子、硫黄原子、単結合又は無架橋であることを示し、
ｍは、各々独立して０～９の整数であり、ここで、ｍの少なくとも１つは２～９の整数
又はｍの少なくとも２つは１～９の整数であり、
Ｎは、１～４の整数であり、ここで、Ｎが２以上の整数の場合、Ｎ個の［ ］内の構造
式は同一であっても異なっていてもよく、
ｒは、各々独立して０～２の整数である。）
［２］
前記式（０）で表される化合物が、下記式（１）で表される化合物である、［１］に記
載の化合物。

（１）
（式（１）中、Ｒ⁰は、前記Ｒ^Yと同義であり、
Ｒ¹は、炭素数１～６０のｎ価の基又は単結合であり、
Ｒ²～Ｒ⁵は、各々独立して、置換基を有していてもよい炭素数１～３０のアルキル基、
置換基を有していてもよい炭素数６～３０のアリール基、置換基を有していてもよい炭素
数２～３０のアルケニル基、置換基を有していてもよい炭素数１～３０のアルコキシ基、
ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基又は水酸基であり、前記
アルキル基、前記アリール基、前記アルケニル基及び前記アルコキシ基は、エーテル結合
、ケトン結合又はエステル結合を含んでいてもよく、ここで、Ｒ²～Ｒ⁵の少なくとも１つ
は少なくとも１つは水酸基であり、またＲ²～Ｒ⁵の少なくとも１つは炭素数２～３０のア
ルケニル基であり、
ｍ²及びｍ³は、各々独立して、０～８の整数であり、
ｍ⁴及びｍ⁵は、各々独立して、０～９の整数であり、但し、ｍ²、ｍ³、ｍ⁴及びｍ⁵は同
時に０になることはなく、ｍ²、ｍ³、ｍ⁴及びｍ⁵の少なくとも１つは２～８若しくは２～
９の整数又はｍ²、ｍ³、ｍ⁴及びｍ⁵の少なくとも２つは１～８若しくは１～９の整数であ
り、
ｎは前記Ｎと同義であり、ここで、ｎが２以上の整数の場合、ｎ個の［ ］内の構造式
は同一であっても異なっていてもよく、
ｐ²～ｐ⁵は、各々独立して、前記ｒと同義である。）
［３］
前記式（０）で表される化合物が、下記式（２）で表される化合物である、［１］に記
載の化合物。

（２）
（式（２）中、Ｒ^0Aは、前記Ｒ^Yと同義であり、
Ｒ^1Aは、炭素数１～３０のｎ^A価の基又は単結合であり、
Ｒ^2Aは、各々独立して、置換基を有していてもよい炭素数１～３０のアルキル基、置換
基を有していてもよい炭素数６～３０のアリール基、置換基を有していてもよい炭素数２
～３０のアルケニル基、置換基を有していてもよい炭素数１～３０のアルコキシ基、ハロ
ゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基又は水酸基であり、前記アル
キル基、前記アリール基、前記アルケニル基及び前記アルコキシ基は、エーテル結合、ケ
トン結合又はエステル結合を含んでいてもよく、ここで、Ｒ^2Aの少なくとも１つは少なく
とも１つは水酸基であり、またＲ^2Aの少なくとも１つは炭素数２～３０のアルケニル基で
あり、
ｎ^Aは、前記Ｎと同義であり、ここで、ｎ^Aが２以上の整数の場合、ｎ^A個の［ ］内の
構造式は同一であっても異なっていてもよく、
Ｘ^Aは、酸素原子、硫黄原子、単結合又は無架橋であることを示し、
ｍ^2Aは、各々独立して、０～７の整数であり、但し、少なくとも１つのｍ^2Aは２～７の
整数又は少なくとも２つのｍ^2Aは１～７の整数であり、
ｑ^Aは、各々独立して、０又は１である。）
［４］
前記式（１）で表される化合物が、下記式（１－１）で表される化合物である、［２］
に記載の化合物。

（１－１）
（式（１－１）中、Ｒ⁰、Ｒ¹、Ｒ⁴、Ｒ⁵、ｎ、ｐ²～ｐ⁵、ｍ⁴及びｍ⁵は、前記と同義であ
り、
Ｒ⁶～Ｒ⁷は、各々独立して、置換基を有していてもよい炭素数１～３０のアルキル基、
置換基を有していてもよい炭素数６～３０のアリール基、置換基を有していてもよい炭素
数２～３０のアルケニル基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基又はチオ
ール基であり、ここで、Ｒ⁶～Ｒ⁷の少なくとも１つは炭素数２～３０のアルケニル基であ
り、
Ｒ¹⁰～Ｒ¹¹は、各々独立して、水素原子であり、
ｍ⁶及びｍ⁷は、各々独立して、０～７の整数であり、但し、ｍ⁴、ｍ⁵、ｍ⁶及びｍ⁷は同
時に０になることはない。）
［５］
前記式（１－１）で表される化合物が、下記式（１－２）で表される化合物である、［
４］に記載の化合物。

（１－２）
（式（１－２）中、Ｒ⁰、Ｒ¹、Ｒ⁶、Ｒ⁷、Ｒ¹⁰、Ｒ¹¹、ｎ、ｐ²～ｐ⁵、ｍ⁶及びｍ⁷は、前
記と同義であり、
Ｒ⁸～Ｒ⁹は、前記Ｒ⁶～Ｒ⁷と同義であり、
Ｒ¹²～Ｒ¹³は、前記Ｒ¹⁰～Ｒ¹¹と同義であり、
ｍ⁸及びｍ⁹は、各々独立して、０～８の整数であり、但し、ｍ⁶、ｍ⁷、ｍ⁸及びｍ⁹は同
時に０になることはない。）
［６］
前記式（２）で表される化合物が、下記式（２－１）で表される化合物である、［３］
に記載の化合物。

（２－１）
（式（２－１）中、Ｒ^0A、Ｒ^1A、ｎ^A、ｑ^A及びＸ^A、は、前記と同義であり、
Ｒ^3Aは、各々独立して、置換基を有していてもよい炭素数１～３０のアルキル基、置換
基を有していてもよい炭素数６～３０のアリール基、置換基を有していてもよい炭素数２
～３０のアルケニル基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基又はチオール
基であり、ここで、Ｒ^3Aの少なくとも１つは炭素数２～３０のアルケニル基であり、
Ｒ^4Aは、各々独立して、水素原子であり、
ｍ^6Aは、各々独立して、０～５の整数である。）
［７］
［１］に記載の化合物をモノマーとして得られる、樹脂。
［８］
下記式（３）で表される構造を有する、［７］に記載の樹脂。

（３）
（式（３）中、Ｌは、置換基を有していてもよい炭素数１～３０の直鎖状、分岐状若しく
は環状のアルキレン基、置換基を有していてもよい炭素数６～３０のアリーレン基、置換
基を有していてもよい炭素数１～３０のアルコキシレン基又は単結合であり、前記アルキ
レン基、前記アリーレン基及び前記アルコキシレン基は、エーテル結合、ケトン結合又は
エステル結合を含んでいてもよく、
Ｒ⁰は、前記Ｒ^Yと同義であり、
Ｒ¹は、炭素数１～６０のｎ価の基又は単結合であり、
Ｒ²～Ｒ⁵は、各々独立して、置換基を有していてもよい炭素数１～３０のアルキル基、
置換基を有していてもよい炭素数６～３０のアリール基、置換基を有していてもよい炭素
数２～３０のアルケニル基、置換基を有していてもよい炭素数１～３０のアルコキシ基、
ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基又は水酸基であり、前記
アルキル基、前記アリール基、前記アルケニル基及び前記アルコキシ基は、エーテル結合
、ケトン結合又はエステル結合を含んでいてもよく、ここで、Ｒ²～Ｒ⁵の少なくとも１つ
は水酸基であり、またＲ²～Ｒ⁵の少なくとも１つは炭素数２～３０のアルケニル基であり
、
ｍ²及びｍ³は、各々独立して、０～８の整数であり、
ｍ⁴及びｍ⁵は、各々独立して、０～９の整数であり、但し、ｍ²、ｍ³、ｍ⁴及びｍ⁵は同
時に０になることはなく、ｍ²、ｍ³、ｍ⁴及びｍ⁵の少なくとも１つは２～８若しくは２～
９の整数又はｍ²、ｍ³、ｍ⁴及びｍ⁵の少なくとも２つは１～８若しくは１～９の整数であ
る。）
［９］
下記式（４）で表される構造を有する、［７］に記載の樹脂。

（４）
（式（４）中、Ｌは、炭素数１～３０の直鎖状若しくは分岐状のアルキレン基又は単結合
であり、
Ｒ^0Aは、前記Ｒ^Yと同義であり、
Ｒ^1Aは、炭素数１～３０のｎ^A価の基又は単結合であり、
Ｒ^2Aは、各々独立して、置換基を有していてもよい炭素数１～３０のアルキル基、置換
基を有していてもよい炭素数６～３０のアリール基、置換基を有していてもよい炭素数２
～３０のアルケニル基、置換基を有していてもよい炭素数１～３０のアルコキシ基、ハロ
ゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基又は水酸基であり、前記アル
キル基、前記アリール基、前記アルケニル基及び前記アルコキシ基は、エーテル結合、ケ
トン結合又はエステル結合を含んでいてもよく、ここで、Ｒ^2Aの少なくとも１つは水酸基
であり、またＲ^2Aの少なくとも１つは炭素数２～３０のアルケニル基であり、
ｎ^Aは、前記Ｎと同義であり、ここで、ｎ^Aが２以上の整数の場合、ｎ^A個の［ ］内の
構造式は同一であっても異なっていてもよく、
Ｘ^Aは、酸素原子、硫黄原子、単結合又は無架橋であることを示し、
ｍ^2Aは、各々独立して、０～７の整数であり、但し、少なくとも１つのｍ^2Aは２～７の
整数又は少なくとも２つのｍ^2Aは１～７の整数であり、
ｑ^Aは、各々独立して、０又は１である。）
［１０］
［１］～［６］のいずれかに記載の化合物及び［７］～［９］のいずれかに記載の樹脂
からなる群より選ばれる１種以上を含有する、組成物。
［１１］
溶媒をさらに含有する、［１０］に記載の組成物。
［１２］
酸発生剤をさらに含有する、［１０］又は［１１］に記載の組成物。
［１３］
酸架橋剤をさらに含有する、［１０］～［１２］のいずれかに記載の組成物。
［１４］
リソグラフィー用膜形成組成物である、［１０］～［１３］のいずれかに記載の組成物
。
［１５］
光学部品形成組成物である、［１０］～［１３］のいずれかに記載の組成物。
［１６］
［１４］に記載の組成物を用いて基板上にフォトレジスト層を形成した後、前記フォト
レジスト層の所定の領域に放射線を照射し、現像を行う工程を含む、レジストパターン形
成方法。
［１７］
［１４］に記載の組成物を用いて基板上に下層膜を形成し、前記下層膜上に、少なくと
も１層のフォトレジスト層を形成した後、前記フォトレジスト層の所定の領域に放射線を
照射し、現像を行う工程を含む、レジストパターン形成方法。
［１８］
［１４］に記載の組成物を用いて基板上に下層膜を形成し、前記下層膜上にレジスト中
間層膜材料を用いて中間層膜を形成し、前記中間層膜上に、少なくとも１層のフォトレジ
スト層を形成する工程、
前記フォトレジスト層の所定の領域に放射線を照射し、現像してレジストパターンを形
成する工程、
前記レジストパターンをマスクとして前記中間層膜をエッチングし、得られた中間層膜
パターンをエッチングマスクとして前記下層膜をエッチングし、得られた下層膜パターン
をエッチングマスクとして基板をエッチングすることにより基板にパターンを形成する工
程、を含む、回路パターン形成方法。 The inventors of the present invention have made intensive studies to solve the problems of the prior art, and found that a compound or resin having a specific structure can solve the problems of the prior art, and have completed the present invention. rice field.
That is, the present invention is as follows.
[1]
A compound represented by the following formula (0).

(0)
(In formula (0), ^RY is a hydrogen atom,
R ^Z is an N-valent group having 1 to 60 carbon atoms or a single bond,
Each R ^T is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
an alkenyl group of up to 30, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl The groups, said alkenyl groups and said alkoxy groups may contain ether linkages, ketone linkages or ester linkages, wherein at least one of ^RT is a hydroxyl group and at least one of ^RT is a carbon number 2 to 30 alkenyl groups,
X represents an oxygen atom, a sulfur atom, a single bond or no cross-linking,
m is each independently an integer from 0 to 9, wherein at least one of m is an integer from 2 to 9 or at least two of m are integers from 1 to 9;
N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas in N [ ] may be the same or different,
Each r is independently an integer of 0-2. )
[2]
The compound according to [1], wherein the compound represented by the formula (0) is a compound represented by the following formula (1).

(1)
(In formula (1), R ⁰ has the same meaning as R ^Y above,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
each of R ² to R ⁵ is independently an optionally substituted alkyl group having 1 to 30 carbon atoms;
optionally substituted C6-30 aryl group, optionally substituted C2-30 alkenyl group, optionally substituted C1-30 an alkoxy group of
a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond. well, at least one of R ² to R ⁵ is at least one hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms,
m ² and m ³ are each independently an integer of 0 to 8;
m ⁴ and m ⁵ are each independently an integer of 0 to 9, provided that m ² , m ³ , m ⁴ and m ⁵ are not 0 at the same time, m ² , m ³ and m ⁴ and at least one of m ⁵ is 2 to 8 or 2 to
an integer of 9 or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers from 1 to 8 or from 1 to 9;
n is the same as the above N, where n is an integer of 2 or more, n structural formulas in [ ] may be the same or different,
p ² to p ⁵ are each independently the same as r above. )
[3]
The compound according to [1], wherein the compound represented by the formula (0) is a compound represented by the following formula (2).

(2)
(In formula (2), R ^0A is synonymous with R ^Y above,
R ^1A is an n ^A -valent group having 1 to 30 carbon atoms or a single bond,
Each R ^2A is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
an alkenyl group of up to 30, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl The groups, said alkenyl groups and said alkoxy groups, may contain ether linkages, ketone linkages or ester linkages, wherein at least one of R ^2A is at least one hydroxyl group and at least one of R ^2A is is an alkenyl group having 2 to 30 carbon atoms,
n ^A has the same definition as the above N, where n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom, a single bond or no cross-linking,
each m ^2A is independently an integer from 0 to 7, with the proviso that at least one m ^2A is an integer from 2 to 7 or at least two m ^2A are an integer from 1 to 7;
q ^A is each independently 0 or 1; )
[4]
The compound represented by the formula (1) is a compound represented by the following formula (1-1) [2]
The compound described in .

(1-1)
(in formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are as defined above;
each of R ⁶ to R ⁷ is independently an optionally substituted alkyl group having 1 to 30 carbon atoms;
optionally substituted C6-C30 aryl group, optionally substituted C2-C30 alkenyl group, halogen atom, nitro group, amino group, carboxylic acid group or thiol a group, wherein at least one of R ⁶ to R ⁷ is an alkenyl group having 2 to 30 carbon atoms;
R ¹⁰ to R ¹¹ are each independently a hydrogen atom,
m ⁶ and m ⁷ are each independently an integer of 0 to 7, provided that m ⁴ , m ⁵ , m ⁶ and m ⁷ are not 0 at the same time. )
[5]
The compound represented by the formula (1-1) is a compound represented by the following formula (1-2), [
4].

(1-2)
(in formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are as defined above;
R ⁸ to R ⁹ have the same definitions as R ⁶ to R ⁷ above;
R ¹² to R ¹³ have the same definitions as R ¹⁰ to R ¹¹ ;
m ⁸ and m ⁹ are each independently an integer of 0 to 8, provided that m ⁶ , m ⁷ , m ⁸ and m ⁹ are not 0 at the same time. )
[6]
The compound represented by the formula (2) is a compound represented by the following formula (2-1) [3]
The compound described in .

(2-1)
(in formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A are as defined above;
Each R ^3A is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
-30 alkenyl groups, halogen atoms, nitro groups, amino groups, carboxylic acid groups or thiol groups, wherein at least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms;
each R ^4A is independently a hydrogen atom,
Each m ^6A is independently an integer of 0-5. )
[7]
A resin obtained by using the compound according to [1] as a monomer.
[8]
The resin according to [7], having a structure represented by the following formula (3).

(3)
(In the formula (3), L is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may have a substituent, 6 to 6 carbon atoms which may have a substituent, 30 arylene group, optionally substituted alkoxylene group having 1 to 30 carbon atoms or a single bond, wherein the alkylene group, the arylene group and the alkoxylylene group are an ether bond, a ketone bond or an ester may contain a bond,
R ⁰ has the same definition as R ^Y above,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
each of R ² to R ⁵ is independently an optionally substituted alkyl group having 1 to 30 carbon atoms;
optionally substituted C6-30 aryl group, optionally substituted C2-30 alkenyl group, optionally substituted C1-30 an alkoxy group of
a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond. well, at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms,
m ² and m ³ are each independently an integer of 0 to 8;
m ⁴ and m ⁵ are each independently an integer of 0 to 9, provided that m ² , m ³ , m ⁴ and m ⁵ are not 0 at the same time, m ² , m ³ and m ⁴ and at least one of m ⁵ is 2 to 8 or 2 to
An integer of 9 or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers of 1-8 or 1-9. )
[9]
The resin according to [7], having a structure represented by the following formula (4).

(4)
(In formula (4), L is a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond,
R ^0A has the same definition as R ^Y above,
R ^1A is an n ^A -valent group having 1 to 30 carbon atoms or a single bond,
Each R ^2A is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
an alkenyl group of up to 30, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl The groups, the alkenyl groups and the alkoxy groups may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R ^2A is a hydroxyl group and at least one of R ^2A is a carbon number 2 to 30 alkenyl groups,
n ^A has the same definition as the above N, where n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom, a single bond or no cross-linking,
each m ^2A is independently an integer from 0 to 7, with the proviso that at least one m ^2A is an integer from 2 to 7 or at least two m ^2A are an integer from 1 to 7;
q ^A is each independently 0 or 1; )
[10]
A composition containing one or more selected from the group consisting of the compound according to any one of [1] to [6] and the resin according to any one of [7] to [9].
[11]
The composition according to [10], further containing a solvent.
[12]
The composition according to [10] or [11], further comprising an acid generator.
[13]
The composition according to any one of [10] to [12], further containing an acid cross-linking agent.
[14]
The composition according to any one of [10] to [13], which is a film-forming composition for lithography.
[15]
The composition according to any one of [10] to [13], which is an optical component-forming composition.
[16]
[14] A method of forming a resist pattern, which comprises forming a photoresist layer on a substrate using the composition according to [14], and then irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer.
[17]
An underlayer film is formed on a substrate using the composition according to [14], and after forming at least one photoresist layer on the underlayer film, a predetermined region of the photoresist layer is irradiated with radiation. and developing a resist pattern.
[18]
Forming an underlayer film on a substrate using the composition according to [14], forming an intermediate layer film on the underlayer film using a resist intermediate layer film material, and forming at least one layer on the intermediate layer film forming a photoresist layer of
a step of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern;
The intermediate layer film is etched using the resist pattern as a mask, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask. A method of forming a circuit pattern, comprising: forming a pattern.

The compounds and resins according to the present invention have high solubility in safe solvents and good heat resistance and etching resistance. Also, the composition containing the compound and/or resin according to the present invention gives a good resist pattern shape.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated. The following embodiments are examples for explaining the present invention, and the present invention is not limited only to these embodiments.

The compound, resin, and composition containing the same in the present embodiment are applicable to wet processes and are useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance. In addition, since the composition of the present embodiment uses a compound or resin having a specific structure that is highly heat-resistant and solvent-soluble, deterioration of the film during high-temperature baking is suppressed, and etching resistance to oxygen plasma etching etc. It is possible to form a resist and an underlayer film which are also excellent in In addition, when an underlayer film is formed, the adhesiveness to the resist layer is excellent, so an excellent resist pattern can be formed.
Furthermore, since it has a high refractive index and suppresses coloration due to heat treatment over a wide range from low to high temperatures, it is also useful as various optical-forming compositions.

[Compound represented by formula (0)]
The compound in this embodiment is represented by the following formula (0).

（０）

(0)

(In formula (0), ^RY is a hydrogen atom,
R ^Z is an N-valent group having 1 to 60 carbon atoms or a single bond,
Each R ^T is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
~30 alkenyl group, optionally substituted alkoxy group having 1 to 30 carbon atoms, halogen atom, nitro group, amino group, carboxylic acid group, thiol group or hydroxyl group, the above alkyl group, the above aryl The groups, the alkenyl groups and the alkoxy groups may contain ether linkages, ketone linkages or ester linkages, wherein at least one of ^RT is a hydroxyl group and at least one of ^RT is a carbon number 2 to 30 alkenyl groups,
X represents an oxygen atom, a sulfur atom, a single bond or no cross-linking,
m is each independently an integer from 0 to 9, wherein at least one of m is an integer from 2 to 9 or at least two of m are integers from 1 to 9;
N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas in N [ ] may be the same or different,
Each r is independently an integer of 0-2. )

^RY is a hydrogen atom. A linear, branched or cyclic alkyl group can be used as the alkyl group. When R ^Y is a hydrogen atom, excellent heat resistance and solvent solubility can be imparted.

R ^Z is an N-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded via R ^Z . N is an integer of 1 to 4, and when N is an integer of 2 or more, N structural formulas in [ ] may be the same or different. The above N-valent group means an alkyl group having 1 to 60 carbon atoms when N = 1, an alkylene group having 1 to 30 carbon atoms when N = 2, N
= 3, an alkanepropyl group with 2 to 60 carbon atoms, and when N = 4, 3 carbon atoms
~60 alkanetetrayl groups. Examples of the N-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. In addition, the above N-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.

Each R ^T is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
an alkenyl group of up to 30, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group, the above alkyl group, the above aryl The group, the alkenyl group, the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one of ^RT is a hydroxyl group and at least one of ^RT is a carbon number It contains 2-30 alkenyl groups. The alkyl group, alkenyl group and alkoxy group may be linear, branched or cyclic groups.

X represents an oxygen atom, a sulfur atom, a single bond, or no cross-linking. When X is an oxygen atom or a sulfur atom, it tends to exhibit high heat resistance, and is preferably an oxygen atom. preferable. From the viewpoint of solubility, X is preferably non-crosslinked. Each m is independently an integer of 0 to 9, and at least one of m is an integer of 2 to 9 or at least two of m is an integer of 1 to 9.

In formula (0), the site represented by the naphthalene structure is a monocyclic structure when r = 0, and r
=1 is a bicyclic structure and r=2 is a tricyclic structure. Each r is independently an integer of 0-2. The numerical range of m described above is determined according to the ring structure determined by r.

[Compound represented by formula (1)]
Compound (0) in the present embodiment is preferably a compound represented by the following formula (1) from the viewpoint of heat resistance and solvent solubility.

（１）

(1)

In formula (1) above, R ⁰ has the same meaning as R ^Y above and is a hydrogen atom. When R ⁰ is a hydrogen atom, the heat resistance tends to be relatively high and the solvent solubility tends to improve.
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded via R ¹ .
each of R ² to R ⁵ is independently an optionally substituted alkyl group having 1 to 30 carbon atoms;
optionally substituted C6-30 aryl group, optionally substituted C2-30 alkenyl group, optionally substituted C1-30 an alkoxy group of
a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond. Well, at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms.
m ² and m ³ are each independently an integer of 0 to 8, m ⁴ and m ⁵ are each independently 0
Integer from ~9. However, m ² , m ³ , m ⁴ and m ⁵ cannot be 0 at the same time. ^{m2 ,} m3
, m ⁴ and at least one of m ⁵ is an integer of 2 to 8 or 2 to 9, or m ² , m ³ , m ⁴ and m ⁵
is an integer of 1-8 or 1-9.
n has the same definition as N above and is an integer of 1-4. Here, when n is an integer of 2 or more, n
Structural formulas in brackets [ ] may be the same or different.
p ² to p ⁵ each independently has the same meaning as r above and is an integer of 0 to 2;

The alkyl group, alkenyl group and alkoxy group may be linear, branched or cyclic groups.

The n-valent group is an alkyl group having 1 to 60 carbon atoms when n = 1, an alkylene group having 1 to 30 carbon atoms when n = 2, and a carbon atom when n = 3. An alkanepropyl group with a number of 2 to 60, and an alkanetetrayl group with a carbon number of 3 to 60 when n=4. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

In addition, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a heteroatom, or an aromatic group having 6 to 60 carbon atoms. Here, the above alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group.

Although the compound represented by the above formula (1) has a relatively low molecular weight, it has a high heat resistance due to the rigidity of its structure, so that it can be used even under high-temperature baking conditions. Moreover, it has tertiary carbon or quaternary carbon in the molecule, so that the crystallinity is suppressed, and it is suitably used as a film-forming composition for lithography that can be used for producing a film for lithography.

In addition, since it has high solubility in safe solvents and good heat resistance and etching resistance,
A resist-forming composition for lithography containing the compound represented by the above formula (1) can give a good resist pattern shape.

Furthermore, since it has a relatively low molecular weight and low viscosity, even if the substrate has a step (especially a fine space or a hole pattern), it can be uniformly filled to every corner of the step and the film can be flattened. As a result, the underlayer film-forming composition for lithography using the same has good embedding and planarization properties. Moreover, since it is a compound having a relatively high carbon concentration, it can also provide high etching resistance.

Furthermore, since the aromatic density is high, the refractive index is high, and coloring is suppressed by heat treatment over a wide range from low temperature to high temperature, so it is also useful as a composition for forming various optical parts. Among them, a compound having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloration, and improving heat resistance and solvent solubility. As optical parts, in addition to film-shaped and sheet-shaped parts, plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic shielding films, It is useful as a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.

（１－１） The compound represented by the above formula (1) is more preferably a compound represented by the following formula (1-1) from the viewpoint of ease of cross-linking and solubility in organic solvents.

(1-1)

In formula (1-1),
R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are as defined above;
each of R ⁶ to R ⁷ is independently an optionally substituted alkyl group having 1 to 30 carbon atoms;
optionally substituted C6-C30 aryl group, optionally substituted C2-C30 alkenyl group, halogen atom, nitro group, amino group, carboxylic acid group or thiol a group, wherein at least one of R ⁶ to R ⁷ is an alkenyl group having 2 to 30 carbon atoms;
R ¹⁰ to R ¹¹ are each independently a hydrogen atom,
m ⁶ and m ⁷ are each independently an integer of 0 to 7, provided that m ⁴ , m ⁵ , m ⁶ and m ⁷ are not 0 at the same time.

Further, the compound represented by the above formula (1-1) is more preferably a compound represented by the following formula (1-2) from the viewpoint of ease of further cross-linking and solubility in organic solvents. .

（１－２）

(1-2)

In formula (1-2),
R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are as defined above;
R ⁸ to R ⁹ have the same definitions as R ⁶ to R ⁷ above;
R ¹² to R ¹³ have the same definitions as R ¹⁰ to R ¹¹ above,
m ⁸ and m ⁹ are each independently an integer of 0-8. However, m ⁶ , m ⁷ , m ⁸ and m ⁹ cannot be 0 at the same time.

In addition, the compound represented by the above formula (1-1) has the following formula (1a
) is also more preferred.

（１ａ）

(1a)

In formula (1a) above, R ⁰ to R ⁵ , m ² to m ⁵ and n have the same meanings as in formula (1) above.

From the viewpoint of solubility in organic solvents, the compound represented by the above formula (1a) is represented by the following formula (1b)
A compound represented by is even more preferable.

（１ｂ）

(1b)

In the above formula (1b), R ⁰ , R ¹ , R ⁴ , R ⁵ , m ⁴ , m ⁵ and n have the same meanings as explained in the above formula (1), and R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , m ⁶ and m ⁷ have the same meanings as those explained in formula (1-1) above.

From the viewpoint of solubility in organic solvents, the compound represented by the above formula (1b) is represented by the following formula (1c)
It is even more preferred that the compound is represented by

（１ｃ）

(1c)

In formula (1c) above, R ⁰ , R ¹ , R ⁶ to R ¹³ , m ⁶ to m ⁹ , and n are the same as defined in formula (1-2) above.

The compound represented by the above formula (1) has the following formula (
Compounds represented by BisF-1) to (BisF-5) are highly preferred.

（ＢｉＦ－１）

（ＢｉＦ－２）

（ＢｉＦ－３）

(BiF-1)

(BiF-2)

(BiF-3)

（ＢｉＦ－４）

(BiF-4)

（ＢｉＦ－５）

(BiF-5)

In the above formulas (BiF-1) to (BiF-5), R ^6' to R ^9' are each independently a hydrogen atom,
optionally substituted C1-30 alkyl group, optionally substituted C6-30 aryl group, optionally substituted C2-30 an alkenyl group, a halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol group, wherein R ^6′ to
At least one of R ^9′ is an alkenyl group having 2 to 30 carbon atoms, and R ¹⁰ to R ¹³ are represented by the above formula (1
It has the same meaning as described in c).

[Method for producing compound represented by formula (0)]
The compound represented by formula (0) in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited. The compound represented by Formula (0) will be described below using the compound represented by Formula (1) as an example.
For example, under normal pressure, biphenols, binaphthols or bianthracenol and corresponding aldehydes are polycondensed under an acid catalyst to obtain a polyphenol compound, followed by at least one phenolic compound of the polyphenol compound. It can be obtained by introducing an allyl group into a hydroxyl group and then heating to cause Claisen rearrangement. Also, if necessary, it can be carried out under pressure.

The allyl group may be introduced at the pre-stage or post-stage of the condensation reaction, or after the production of the resin described below.

Examples of the biphenols include biphenol, methylbiphenol, methoxybinaphthol and the like, but are not particularly limited thereto. These are one kind alone,
Or it can be used in combination of 2 or more types. Among these, it is more preferable to use biphenol from the viewpoint of stable supply of raw materials.

Examples of the binaphthols include, but are not limited to, binaphthol, methylbinaphthol, methoxybinaphthol, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is more preferable to use binaphthol from the viewpoint of increasing the carbon atom concentration and improving the heat resistance.

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, Naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural and the like can be mentioned, but are not particularly limited to these. These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of imparting high heat resistance, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracene It is preferable to use carbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural, and from the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenyl Aldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde and furfural are more preferably used.

As the aldehyde, it is preferable to use an aldehyde having an aromatic ring from the viewpoint of having both high heat resistance and high etching resistance.

The acid catalyst used in the above reaction can be appropriately selected from known ones and used.
It is not particularly limited. As such acid catalysts, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, organic acids such as naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid and phosphomolybdic acid However, it is not particularly limited to these. Among these
Organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is more preferred from the viewpoint of production such as availability and ease of handling. For the acid catalyst, 1
The seeds can be used singly or in combination of two or more. In addition, the amount of acid catalyst used is
It can be set appropriately according to the type of raw material and catalyst used, reaction conditions, etc., and is not particularly limited, but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material.

A reaction solvent may be used in the above reaction. The reaction solvent is not particularly limited as long as the reaction between the aldehydes to be used and the biphenols, binaphthols or bianthracenediol proceeds, and can be appropriately selected from known solvents and used. Examples of reaction solvents include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and mixed solvents thereof. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.

In addition, the amount of these reaction solvents used can be appropriately set according to the types of raw materials and catalysts used, as well as the reaction conditions, etc., and is not particularly limited.
It is preferably in the range of 00 parts by mass. Furthermore, the reaction temperature in the above reaction can be appropriately selected according to the reactivity of the reaction raw materials, and is not particularly limited, but is usually 10 to 200°C.
is in the range of

In order to obtain a polyphenol compound, the reaction temperature is preferably higher, specifically 60
A range of ~200°C is preferred. In addition, the reaction method can be appropriately selected and used from known methods, and is not particularly limited. Alternatively, a method of dropping bianthracenediol or aldehydes in the presence of a catalyst may be used.
After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, etc. present in the system, a general method such as raising the temperature of the reactor to 130 to 230 ° C. and removing volatile matter at about 1 to 50 mmHg is adopted. Thus, the target compound can be isolated.

As preferable reaction conditions, 1 mol to excess of biphenols, binaphthols or bianthracenediol and 0.001 to 1 mol of an acid catalyst are used per 1 mol of aldehydes, and the reaction temperature is normal pressure, 50 to 150°C. for about 20 minutes to 100 hours.

After completion of the reaction, the desired product can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, cooled to room temperature, filtered and separated,
The obtained solid is filtered, dried, separated and purified from the by-products by column chromatography, the solvent is distilled off, filtered, and dried to obtain the target compound represented by the above formula (1). can be obtained.

A method of introducing an allyl group into at least one phenolic hydroxyl group of a polyphenol compound is also known. For example, an allyl group can be introduced into at least one phenolic hydroxyl group of the above compound as follows.

A compound for introducing an allyl group can be synthesized or easily obtained by a known method.
Examples include allyl chloride, allyl bromide, and allyl iodide, but are not particularly limited to these.

First, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, or the like. Subsequently, in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, etc., the mixture is reacted at normal pressure at 20 to 150° C. for 6 to 72 hours. After neutralizing the reaction solution with an acid and adding distilled water to precipitate a white solid, the separated solid is washed with distilled water, or the solvent is evaporated to dryness and washed with distilled water if necessary, By drying, a compound in which a hydrogen atom of a hydroxy group is substituted with an allyl group can be obtained.

Thereafter, by heating, the allyl group introduced to the phenolic hydroxyl group can be transferred by Claisen rearrangement.

In this embodiment, the allyl group reacts in the presence of radicals or acids/alkalis to change the solubility in acids, alkalis or organic solvents used in coating solvents and developers. The allyl-substituted group preferably has the property of undergoing a chain reaction in the presence of radicals or acids/alkalis in order to enable pattern formation with higher sensitivity and resolution.

[Resin obtained by using the compound represented by the formula (0) as a monomer]
The compound represented by the above formula (0) can be used as it is as a composition (hereinafter also simply referred to as "composition") used for forming films for lithography and optical parts.
A resin obtained by using the compound represented by the above formula (0) as a monomer can also be used as the composition. The resin is obtained, for example, by reacting the compound represented by the above formula (0) with a crosslinkable compound. A resin obtained by using the compound represented by the formula (0) as a monomer and a resin obtained by using the compound represented by the formula (1) as a monomer are described below as examples.

Examples of the resin obtained by using the compound represented by the above formula (1) as a monomer include those having a structure represented by the following formula (3). That is, the composition in this embodiment may contain a resin having a structure represented by the following formula (3).

（３）

(3)

In formula (3), L is an optionally substituted alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms which may be substituted, and a substituent carbon number 1
to 30 alkoxylene groups or single bonds, and the alkylene group, the arylene group, and the alkoxylylene group may contain an ether bond, a ketone bond, or an ester bond. Further, the alkylene group and alkoxylylene group may be linear, branched or cyclic groups.
R ⁰ , R ¹ , R ² to R ⁵ , m ² and m ³ , m ⁴ and m ⁵ , p ² to p ⁵ and n are the same as defined in formula (1) above.
However, m ² , m ³ , m ⁴ and m ⁵ cannot be 0 at the same time, and at least one of m ² , m ³ , m ⁴ and m ⁵ is an integer of 2 to 8 or 2 to 9, or m ² , m ³ , m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9, at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms.

[Method for producing a resin obtained by using a compound represented by formula (1) as a monomer]
The resin in this embodiment is obtained by reacting the compound represented by the above formula (1) with a compound having cross-linking reactivity. As the cross-linkable compound, known compounds can be used without particular limitation as long as they can oligomerize or polymerize the compound represented by the above formula (1). Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.

Specific examples of the resin having the structure represented by the above formula (3) include, for example, a condensation reaction of the compound represented by the above formula (1) with an aldehyde and/or ketone, which is a compound having cross-linking reactivity. and the like.

Examples of aldehydes used in novolac-forming the compound represented by formula (1) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Examples include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural and the like. Examples of ketones include the ketones described above. Among these, formaldehyde is more preferred. In addition, these aldehydes and/or ketones can be used individually by 1 type or in combination of 2 or more types. The amount of the aldehyde and/or ketone used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 1 mol of the compound represented by the formula (1). 0.5 to 2 mol.

An acid catalyst can also be used in the condensation reaction between the compound represented by formula (1) and the aldehyde and/or ketone. The acid catalyst used here is not particularly limited and can be appropriately selected from known ones. As such acid catalysts, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, Organic acids such as naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or silicotungstic acid, phosphotungstic acid,
Examples include solid acids such as silicomolybdic acid and phosphomolybdic acid, but are not particularly limited thereto. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of production such as availability and ease of handling. In addition, about an acid catalyst, it can be used individually by 1 type or in combination of 2 or more types.

In addition, the amount of the acid catalyst used can be appropriately set according to the type of raw material and catalyst to be used, the reaction conditions, etc., and is not particularly limited.
Parts by mass are preferred. However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene Aldehydes are not necessarily required in the case of a copolymerization reaction with a compound having a non-conjugated double bond such as limonene.

A reaction solvent can also be used in the condensation reaction between the compound represented by formula (1) and the aldehyde and/or ketone. As the reaction solvent in this polycondensation, it can be appropriately selected and used from among known ones, and is not particularly limited, but examples thereof include water, methanol,
Ethanol, propanol, butanol, tetrahydrofuran, dioxane, mixed solvents thereof, and the like are included. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.

In addition, the amount of these solvents used can be appropriately set according to the types of raw materials and catalysts used, as well as the reaction conditions, etc., and is not particularly limited.
It is preferably in the range of parts by mass. Furthermore, the reaction temperature can be appropriately selected according to the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200°C. note that,
The reaction method can be appropriately selected from known methods and is not particularly limited, but a method of charging the compound represented by the above formula (1), an aldehyde and/or ketones, and a catalyst all at once,
A method of dropping the compound represented by the above formula (1), aldehyde and/or ketones in the presence of a catalyst can be mentioned.

After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, etc. present in the system, a general method such as raising the temperature of the reactor to 130 to 230 ° C. and removing volatile matter at about 1 to 50 mmHg is adopted. As a result, the target novolak resin can be isolated.

Here, the resin having the structure represented by the above formula (3) may be a homopolymer of the compound represented by the above formula (1), but may be a copolymer with other phenols. may Examples of copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Examples include, but are not limited to, propylphenol, pyrogallol, thymol, and the like.

Moreover, the resin having the structure represented by the above formula (3) may be one obtained by copolymerizing with a polymerizable monomer other than the other phenols described above. Examples of such copolymerizable monomers include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, and 4-vinylcyclohexene. , norbornadiene, vinylnorbornaene, pinene, limonene and the like, but are not particularly limited thereto. Note that the above formula (
3) Even if the resin having the structure represented by the above formula (1) is a two or more (for example, two to four) copolymer of the compound represented by the above formula (1) and the above-described phenol, Even in a binary or more (for example, 2 to quaternary) copolymer of the compound represented by the above formula (1) and the above-described copolymerization monomer, the compound represented by the above formula (1) and the above-described It may be a ternary or higher (for example, ternary to quaternary) copolymer of the phenols and the above-described copolymerizable monomers.

The molecular weight of the resin having the structure represented by the above formula (3) is not particularly limited, but the polystyrene equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20, 000. In addition, from the viewpoint of increasing the cross-linking efficiency and suppressing volatile components during baking, the resin having the structure represented by the above formula (3) has a degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of 1.2. It is preferably within the range of ~7. The above Mw and Mn can be determined by the method described in Examples below.

It is preferable that the resin having the structure represented by the above formula (3) has high solubility in a solvent from the viewpoint of easier application of a wet process. More specifically, 1
When using -methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is preferably 10% by mass or more. Here, the solubility in PGME and/or PGMEA is defined as "mass of resin÷(mass of resin+mass of solvent)×100 (mass %)". For example, when 10 g of the resin dissolves in 90 g of PGMEA, PGME of the resin
The solubility in A is "10% by mass or more", and if it does not dissolve, it is "less than 10% by mass".

[Compound represented by formula (2)]
From the viewpoint of heat resistance and solvent solubility, the compound represented by formula (0) in the present embodiment is
A compound represented by the following formula (2) is preferable.

（２）

(2)

In formula (2), R ^0A has the same definition as R ^Y above, and is a hydrogen atom.
R ^1A is an n ^A -valent group having 1 to 30 carbon atoms or a single bond,
Each R ^2A is independently an optionally substituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms which may be substituted. An aryl group, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, carboxylic an acid group, a thiol group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond,
At least one of R ^2A is a hydroxyl group, and at least one of R ^2A is an alkenyl group having 2 to 30 carbon atoms.
n ^A has the same definition as N above and is an integer of 1 to 4, wherein in formula (2), when n ^A is an integer of 2 or more, n ^A structural formulas in [ ] are the same There may be or may be different.
Each X ^A independently represents an oxygen atom, a sulfur atom, a single bond, or no bridge. Here, X ^A is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom, since it tends to exhibit excellent heat resistance. X ^A is preferably non-crosslinked from the viewpoint of solubility.
Each m ^2A is independently an integer of 0-6. However, at least one m ^2A is an integer of 2-6 or at least two m ^2A is an integer of 1-6.
q ^A is each independently 0 or 1;

The n-valent group is an alkyl group having 1 to 60 carbon atoms when n = 1, an alkylene group having 1 to 30 carbon atoms when n = 2, and a carbon atom when n = 3. An alkanepropyl group with a number of 2 to 60, and an alkanetetrayl group with a carbon number of 3 to 60 when n=4. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

In addition, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms. Here, the above alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group.

In addition, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a heteroatom, or an aromatic group having 6 to 30 carbon atoms. Here, the above alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group.

The compound represented by the above formula (2) has a relatively low molecular weight, but has a high heat resistance due to the rigidity of its structure, so that it can be used even under high-temperature baking conditions. Moreover, it has tertiary carbon or quaternary carbon in the molecule, so that the crystallinity is suppressed, and it is suitably used as a film-forming composition for lithography that can be used for producing a film for lithography.

In addition, since it has high solubility in safe solvents and good heat resistance and etching resistance,
A resist-forming composition for lithography containing the compound represented by the above formula (2) can provide a good resist pattern shape.

Furthermore, since it has a relatively low molecular weight and low viscosity, even if the substrate has a step (especially a fine space or a hole pattern), it can be uniformly filled to every corner of the step and the film can be flattened. As a result, the underlayer film-forming composition for lithography using the same has good embedding and planarization properties. Moreover, since it is a compound having a relatively high carbon concentration, it can also provide high etching resistance.

Furthermore, since the aromatic density is high, the refractive index is high, and coloring is suppressed by heat treatment over a wide range from low temperature to high temperature, so it is also useful as a composition for forming various optical parts. Among them, a compound having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloration, and improving heat resistance and solvent solubility. As optical parts, in addition to film-shaped and sheet-shaped parts, plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic shielding films, It is useful as a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.

The compound represented by the above formula (2) is more preferably a compound represented by the following formula (2-1) from the viewpoint of ease of cross-linking and solubility in organic solvents.

（２－１）

(2-1)

In formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A are the same as defined in formula (2) above.
R ^3A is an optionally substituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, substituted an alkenyl group having 2 to 30 carbon atoms which may have a group, a halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol group, which may be the same or different in the same naphthalene ring or benzene ring; may wherein at least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms,
each R ^4A is independently a hydrogen atom,
Each m ^6A is independently an integer of 0-5.

When the compound represented by the above formula (2-1) is used as a film-forming composition for lithography for an alkaline development positive resist or an organic development negative resist, at least one of R ^4A is an acid dissociable group is. On the other hand, when the compound represented by formula (2-1) is used as a film-forming composition for alkali development negative resist lithography, a film-forming composition for underlayer film lithography or an optical component-forming composition, R At least one of ^4A is a hydrogen atom.

In addition, the compound represented by the above formula (2-1) has the following formula (2a
) is more preferred.

（２ａ）

(2a)

In the above formula (2a), X ^A , R ^0A to R ^2A , m ^2A and n ^A have the same meanings as explained in the above formula (2).

Further, the compound represented by the above formula (2-1) is more preferably a compound represented by the following formula (2b) from the viewpoint of solubility in organic solvents.

（２ｂ）

(2b)

In the above formula (2b), X ^A , R ^0A , R ^1A , R ^3A , R ^4A , m ^6A and n ^A are the above formula (2-1)
are synonymous with those described in .

Further, the compound represented by the above formula (2-1) is more preferably a compound represented by the following formula (2c) from the viewpoint of solubility in organic solvents.

（２ｃ）

(2c)

In formula (2c) above, X ^A , R ^0A , R ^1A , R ^3A , R ^4A , m ^6A and n ^A are
are synonymous with those described in .

The compound represented by the above formula (2) has the following formula (
Compounds represented by BisN-1) to (BisN-4) and (XBisN-1) to (XBisN-3) are highly preferred.

（ＢｉｓＮ－１）

（ＢｉｓＮ－２）

（ＢｉｓＮ－３）

（ＢｉｓＮ－４）

（ＸＢｉｓＮ－１）

（ＸＢｉｓＮ－２）

（ＸＢｉｓＮ－３）
上記式（ＢｉｓＮ－１）～（ＢｉｓＮ－４）及び（ＸＢｉｓＮ－１）～（ＸＢｉｓＮ－
３）中、Ｒ^3A及びＲ^4Aは上記式（２－１）で説明したものと同義である。但し、Ｒ^3Aの少
なくとも１つは炭素数２～３０のアルケニル基である。

(BisN-1)

(BisN-2)

(BisN-3)

(BisN-4)

(XBisN-1)

(XBisN-2)

(XBisN-3)
The above formulas (BisN-1) ~ (BisN-4) and (XBisN-1) ~ (XBisN-
In 3), R ^3A and R ^4A have the same meanings as explained in formula (2-1) above. At least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms.

[Method for producing compound represented by formula (2)]
The compound represented by Formula (2) in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited.
For example, under normal pressure, phenols, naphthols and corresponding aldehydes or ketones are polycondensed under an acid catalyst to obtain a polyphenol compound, followed by at least one phenolic hydroxyl group of the polyphenol compound. can be obtained by introducing an allyl group into , followed by Claisen rearrangement by heating. Also, if necessary, it can be carried out under pressure.

The allyl group may be introduced at the pre-stage or post-stage of the condensation reaction, or after the production of the resin described below.

The naphthols are not particularly limited, and examples thereof include naphthol, methylnaphthol, methoxynaphthol, naphthalenediol, etc. Among them, naphthalenediol is preferably used from the viewpoint that a xanthene structure can be easily formed. .

The above phenols are not particularly limited, and examples thereof include phenol, methylphenol, methoxybenzene, catechol, resorcinol, hydroquinone, trimethylhydroquinone and the like.

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, Naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural and the like can be mentioned, but are not particularly limited to these. These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of imparting high heat resistance, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracene It is preferable to use carbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural, and from the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenyl Aldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde and furfural are more preferably used.

The acid catalyst used in the above reaction can be appropriately selected from known ones and used.
It is not particularly limited. The acid catalyst can be appropriately selected from well-known inorganic acids and organic acids.
Organic acids such as toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, etc. solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid; Among these, it is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of production such as availability and ease of handling. About an acid catalyst, it can be used individually by 1 type or in combination of 2 or more types.

A reaction solvent may be used in the above reaction. The reaction solvent is not particularly limited as long as the reaction between the aldehydes and naphthols used proceeds. Examples include water, methanol,
Ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof can be used. The amount of the reaction solvent is not particularly limited, for example, reaction raw material 1
It ranges from 0 to 2000 parts by weight per 00 parts by weight.

The reaction temperature is not particularly limited and can be appropriately selected according to the reactivity of the reaction raw materials, but is preferably in the range of 10 to 200°C. From the viewpoint of synthesizing the compound represented by formula (2) in the present embodiment with good selectivity, the temperature is preferably low, and more preferably in the range of 10 to 60°C.

The reaction method is not particularly limited, but examples thereof include a method of charging naphthols, aldehydes or ketones, and a catalyst all at once, and a method of dropping naphthols or aldehydes in the presence of a catalyst. After completion of the polycondensation reaction, in order to remove unreacted raw materials, catalysts, etc. present in the system, the temperature of the reactor can be raised to 130 to 230° C., and volatile matter can be removed at about 1 to 50 mmHg. .

The amount of the raw material is not particularly limited, but for example, 2 mol to excess of naphthols and the like and 0.001 to 1 mol of an acid catalyst are used with respect to 1 mol of aldehydes, and at normal pressure, 20 to 60 ° C. It is preferable to react for about 20 minutes to 100 hours at .

After completion of the reaction, the desired product is isolated by a known method. The method for isolating the target product is not particularly limited. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, cooled to room temperature, filtered and separated, and the resulting solid After filtering and drying the product, it is separated and purified from by-products by column chromatography, followed by distilling off the solvent, filtering and drying to isolate the target compound.

A method of introducing an allyl group into at least one phenolic hydroxyl group of a polyphenol compound is also known.
For example, an allyl group can be introduced into at least one phenolic hydroxyl group of the above compound as follows.

A compound for introducing an allyl group can be synthesized by a known method or easily obtained, and examples thereof include allyl chloride, allyl bromide, and allyl iodide, but are not particularly limited to these.

First, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, or the like. Subsequently, in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, etc., the mixture is reacted at normal pressure at 20 to 150° C. for 6 to 72 hours. After neutralizing the reaction solution with an acid and adding distilled water to precipitate a white solid, the separated solid is washed with distilled water, or the solvent is evaporated to dryness and washed with distilled water if necessary, By drying, a compound in which a hydrogen atom of a hydroxy group is substituted with an allyl group can be obtained.

In this embodiment, the allyl group reacts in the presence of radicals or acids/alkalis to change the solubility in acids, alkalis or organic solvents used in coating solvents and developers. The allyl-substituted group preferably has the property of undergoing a chain reaction in the presence of radicals or acids/alkalis in order to enable pattern formation with higher sensitivity and resolution.

Thereafter, by heating, the allyl group introduced to the phenolic hydroxyl group can be transferred by Claisen rearrangement.

[Resin obtained by using the compound represented by the formula (2) as a monomer]
The compound represented by the above formula (2) can be used as it is as a film-forming composition for lithography or a composition used for forming optical parts. Also, a resin obtained by using the compound represented by the above formula (2) as a monomer can be used as the composition. The resin
For example, it can be obtained by reacting the compound represented by the above formula (2) with a compound having cross-linking reactivity.

Examples of the resin obtained by using the compound represented by the above formula (2) as a monomer include those having a structure represented by the following formula (4). That is, the composition in this embodiment may contain a resin having a structure represented by the following formula (4).

（４）

(4)

In formula (4), L is a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond.
R ^0A , R ^1A , R ^2A , m ^2A , n ^A , q ^A and ^XA have the same definitions as in formula (2) above;
However, when n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different, and at least one m ^2A is an integer of 2 to 6 or at least two m ^2A is an integer of 1 to 6, at least one of R ^2A is a hydroxyl group, and at least one has 2 to 3 carbon atoms;
0 alkenyl group.

[Method for producing a resin obtained by using a compound represented by formula (2) as a monomer]
The resin in this embodiment is obtained by reacting the compound represented by the above formula (2) with a compound having cross-linking reactivity. As the cross-linkable compound, known compounds can be used without particular limitation as long as they can oligomerize or polymerize the compound represented by the above formula (2). Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.

Specific examples of the resin having the structure represented by the above formula (4) include, for example, a condensation reaction of the compound represented by the above formula (2) with an aldehyde and/or ketone, which is a compound having cross-linking reactivity. and the like.

Examples of aldehydes used in novolac-forming the compound represented by the above formula (2) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Examples include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural and the like. Examples of ketones include the ketones described above. Among these, formaldehyde is more preferred. In addition, these aldehydes and/or ketones can be used individually by 1 type or in combination of 2 or more types. The amount of the aldehyde and/or ketone used is not particularly limited, but it is preferably 0.2 to 5 mol, more preferably 1 mol of the compound represented by the above formula (2). 0.5 to 2 mol.

An acid catalyst can also be used in the condensation reaction between the compound represented by formula (2) and the aldehyde and/or ketone. The acid catalyst used here is not particularly limited and can be appropriately selected from known ones. As such acid catalysts, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, Organic acids such as naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or silicotungstic acid, phosphotungstic acid,
Examples include solid acids such as silicomolybdic acid and phosphomolybdic acid, but are not particularly limited thereto. Among these, organic acids or solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of production such as availability and ease of handling. In addition, about an acid catalyst, it can be used individually by 1 type or in combination of 2 or more types.

In addition, the amount of the acid catalyst used can be appropriately set according to the type of raw material and catalyst used, the reaction conditions, etc., and is not particularly limited.
Parts by mass are preferred. However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene Aldehydes are not necessarily required in the case of a copolymerization reaction with a compound having a non-conjugated double bond such as limonene.

A reaction solvent can also be used in the condensation reaction between the compound represented by formula (2) and the aldehyde and/or ketone. As the reaction solvent in this polycondensation, it is possible to appropriately select and use it from known ones, and it is not particularly limited, but examples include water, methanol,
Ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof can be used. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.

In addition, the amount of these solvents used can be appropriately set according to the type of raw materials and catalysts used, the reaction conditions, etc., and is not particularly limited.
It is preferably in the range of parts by mass. Furthermore, the reaction temperature can be appropriately selected according to the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200°C. note that,
The reaction method can be appropriately selected from known methods and is not particularly limited, but a method of collectively charging the compound represented by the above formula (2), an aldehyde and/or ketones, and a catalyst,
A method of dropping a compound represented by the above formula (2), an aldehyde and/or ketones in the presence of a catalyst may be mentioned.

After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, etc. present in the system, a general method such as raising the temperature of the reactor to 130 to 230 ° C. and removing volatile matter at about 1 to 50 mmHg is adopted. As a result, the target novolak resin can be isolated.

Here, the resin having the structure represented by the above formula (4) may be a homopolymer of the compound represented by the above formula (2), but may be a copolymer with other phenols. may Examples of copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Examples include, but are not limited to, propylphenol, pyrogallol, thymol, and the like.

Moreover, the resin having the structure represented by the above formula (4) may be one obtained by copolymerizing with a polymerizable monomer other than the other phenols described above. Examples of such copolymerizable monomers include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, and 4-vinylcyclohexene. , norbornadiene, vinylnorbornaene, pinene, limonene and the like, but are not particularly limited thereto. Note that the above formula (
4) Even if the resin having the structure represented by formula (2) above is a two or more (for example, two to four) copolymer of the compound represented by the above formula (2) and the above-described phenol, Even if the copolymer of the compound represented by the above formula (2) and the above-described copolymerization monomer (for example, a two- to four-component system) is a copolymer, the compound represented by the above formula (2) and the above-described It may be a ternary or higher (for example, ternary to quaternary) copolymer of the phenols and the above-described copolymerizable monomers.

The molecular weight of the resin having the structure represented by the above formula (4) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, more preferably 750 to 750. 20,000. In addition, from the viewpoint of increasing the cross-linking efficiency and suppressing volatile components during baking, the resin having the structure represented by the above formula (4) has a degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of 1.2. It is preferably within the range of ~7. The above Mw and Mn can be determined by the method described in Examples below.

It is preferable that the resin having the structure represented by the above formula (4) has high solubility in a solvent from the viewpoint of easier application of a wet process. More specifically, 1
When using -methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is preferably 10% by mass or more. Here, the solubility in PGME and/or PGMEA is defined as "mass of resin÷(mass of resin+mass of solvent)×100 (mass %)". For example, when 10 g of the resin dissolves in 90 g of PGMEA, PGME of the resin
The solubility in A is "10% by mass or more", and if it does not dissolve, it is "less than 10% by mass".

[Method for Purifying Compound and/or Resin]
The method for purifying the compound and/or resin in the present embodiment is at least one of the compound represented by the above formula (0) or the resin obtained by using the compound represented by the above formula (0) as a monomer, more specifically is a compound represented by the above formula (1), a resin obtained by using the compound represented by the above formula (1) as a monomer, a compound represented by the above formula (2), and a compound represented by the above formula (2) A step of dissolving one or more selected from resins obtained by using a compound as a monomer in a solvent to obtain a solution (S); or a step of extracting impurities in the resin (first extraction step), and the solution (S)
includes solvents optionally immiscible with water.
In the first extraction step, the resin is the compound represented by the formula (1) and / or the formula (2
) and a compound having cross-linking reactivity. According to the purification method of the present embodiment, it is possible to reduce the contents of various metals that may be contained as impurities in the compound or resin having the specific structure described above.
More specifically, in the purification method of the present embodiment, the compound and/or the resin are
A solution (S) can be obtained by dissolving in an organic solvent that is arbitrarily immiscible with water, and the solution (S) can be brought into contact with an acidic aqueous solution for extraction treatment. As a result, after the metal content in the solution (S) is transferred to the aqueous phase, the organic phase and the aqueous phase are separated to obtain a compound and/or resin with a reduced metal content.

The compounds and/or resins used in the purification method of the present embodiment may be used alone or in combination of two or more. Moreover, the above compounds and resins may contain various surfactants, various cross-linking agents, various acid generators, various stabilizers, and the like.

The solvent arbitrarily immiscible with water used in the purification method of the present embodiment is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable. Specifically, the solubility in water at room temperature is less than 30%, more preferably less than 20%, even more preferably less than 10%. The amount of the organic solvent used is preferably 1 to 100 times the mass of the total amount of the compound and resin used.

Specific examples of water-immiscible solvents include, but are not limited to, ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate, n-butyl acetate and isoamyl acetate; methyl ethyl ketone and methyl isobutyl; Ketones such as ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone; ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl glycol ether acetates such as ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as methylene chloride and chloroform. . Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethyl acetate are preferable, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferable, and methyl Isobutyl ketone and ethyl acetate are more preferred. Methyl isobutyl ketone, ethyl acetate, and the like have relatively high saturated solubility in the above compounds and resins containing the compounds as constituents, and relatively low boiling points. It becomes possible to reduce the load in the process. Each of these solvents can be used alone, or two or more of them can be used in combination.

The acidic aqueous solution used in the purification method of the present embodiment is appropriately selected from aqueous solutions in which generally known organic compounds or inorganic compounds are dissolved in water. Examples of acidic aqueous solutions include, but are not limited to, mineral acid aqueous solutions obtained by dissolving mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid in water; acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, and fumaric acid. , maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and the like dissolved in water.
These acidic aqueous solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, 1 selected from the group consisting of tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid
It is preferably an aqueous solution of organic acids of at least 1 species, more preferably aqueous solutions of sulfuric acid, nitric acid, and carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and citric acid, and more preferably aqueous solutions of sulfuric acid, oxalic acid, tartaric acid, and citric acid. is even more preferred. Polyvalent carboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate with metal ions to produce a chelating effect, and therefore tend to remove metals more effectively. Moreover, the water used here is preferably water with a low metal content, such as ion-exchanged water, in line with the purpose of the purification method of the present embodiment.

Although the pH of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, it is preferable to adjust the acidity of the aqueous solution in consideration of the effects on the above compounds and resins. The pH of the acidic aqueous solution is usually about 0 to 5, preferably about 0 to 3.

The amount of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, but from the viewpoint of reducing the number of extractions for removing metals, and from the viewpoint of ensuring operability in consideration of the total liquid volume, use It is preferable to adjust the amount. From the above viewpoint, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, relative to 100% by mass of the solution (S).

In the purification method of the present embodiment, by bringing the acidic aqueous solution and the solution (S) into contact, the metal component can be extracted from the compound or the resin in the solution (S).

In the purification method of the present embodiment, the solution (S) preferably further contains an organic solvent arbitrarily miscible with water. When the solution (S) contains an organic solvent that is arbitrarily miscible with water, the amount of the compound and/or resin charged can be increased, the liquid separation is improved, and purification can be performed with high pot efficiency. tends to be possible. The method of adding the organic solvent arbitrarily miscible with water is not particularly limited. Any method of adding after contact may be used. Among these, the method of adding to a solution containing an organic solvent in advance is preferable from the viewpoint of the workability of the operation and the ease of controlling the amount to be charged.

The organic solvent arbitrarily miscible with water used in the purification method of the present embodiment is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable. The amount of the organic solvent arbitrarily miscible with water is not particularly limited as long as the solution phase and the aqueous phase are separated, but the total amount of the compound and resin used is 0.1 to 100 times by mass. , more preferably 0.1 to 50 times by mass, even more preferably 0.1 to 20 times by mass.

Specific examples of the organic solvent optionally miscible with water used in the purification method of the present embodiment include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol, and isopropanol. ketones such as acetone and N-methylpyrrolidone; aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether; mentioned. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferred, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferred. Each of these solvents can be used alone, or two or more of them can be used in combination.

The temperature for the extraction treatment is usually 20 to 90°C, preferably 30 to 80°C. The extraction operation is carried out, for example, by mixing well by stirring or the like, and then allowing the mixture to stand still. As a result, the metal content contained in the solution (S) migrates to the aqueous phase. In addition, this operation reduces the acidity of the solution, thereby suppressing deterioration of the compound and/or the resin.

The mixed solution is separated into a solution phase containing a compound and/or resin and a solvent and an aqueous phase by standing still, and the solution phase is recovered by decantation or the like. The time for standing is not particularly limited, but it is preferable to adjust the time for standing from the viewpoint of better separation of the solution phase containing the solvent and the aqueous phase. Usually, the standing time is 1 minute or more, preferably 10 minutes.
minutes or longer, preferably 30 minutes or longer. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating multiple times.

In the purification method of the present embodiment, after the first extraction step, the solution phase containing the compound or the resin is further brought into contact with water to extract impurities in the compound or the resin (second extraction step). Specifically, for example, after performing the extraction treatment using an acidic aqueous solution, the solution phase containing the recovered compound and/or resin and solvent extracted from the aqueous solution is further subjected to extraction treatment with water. is preferred. This extraction treatment with water is not particularly limited, but can be carried out, for example, by mixing the solution phase and water well by stirring or the like, and then allowing the resulting mixed solution to stand still. Since the mixed solution after standing is separated into a solution phase containing a compound and/or resin and a solvent and an aqueous phase, the solution phase can be recovered by decantation or the like.

Moreover, the water used here is preferably water with a low metal content, such as ion-exchanged water, in line with the purpose of the present embodiment. The extraction process may be performed only once, but mixing,
It is also effective to repeat the operation of standing and separating a plurality of times. In the extraction process, conditions such as the ratio of both used, temperature, time, etc. are not particularly limited, but may be the same as in the case of the contact process with the acidic aqueous solution.

Water that may be mixed in the solution containing the compound and/or resin and solvent thus obtained can be easily removed by performing an operation such as distillation under reduced pressure. Moreover, if necessary, a solvent can be added to the above solution to adjust the concentration of the compound and/or the resin to an arbitrary concentration.

The method for isolating the compound and/or resin from the resulting solution containing the compound and/or resin and solvent is not particularly limited, and known methods such as removal under reduced pressure, separation by reprecipitation, and combinations thereof. can be done with If necessary, concentration operation, filtration operation, centrifugation operation,
A known treatment such as a drying operation can be performed.

[Composition]
The composition in the present embodiment is a compound represented by the above formula (0) and a resin obtained by using the compound represented by the above formula (0) as a monomer, more specifically represented by the above formula (1) A group consisting of a compound, a resin obtained by using the compound represented by the above formula (1) as a monomer, a compound represented by the above formula (2), and a resin obtained by using the compound represented by the above formula (2) as a monomer. Contains one or more selected from

The composition of this embodiment can be a film-forming composition for lithography or an optical component-forming composition.

[Film-forming composition for lithography for chemically amplified resist applications]
The film-forming composition for lithography for chemically amplified resist applications in the present embodiment (hereinafter also referred to as "resist composition") comprises the compound represented by the above formula (0) and the above formula (0)
A resin obtained by using a compound represented by a monomer, more specifically a compound represented by the above formula (1), a resin obtained by using a compound represented by the above formula (1) as a monomer, the above formula (2)
and one or more selected from the group consisting of resins obtained by using the compound represented by the above formula (2) as a monomer, as a resist base material.

Moreover, the composition (resist composition) in the present embodiment preferably further contains a solvent. Examples of the solvent include, but are not limited to, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate. ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono - propylene glycol monoalkyl ether acetates such as n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, lactic acid n -Lactic acid esters such as butyl and n-amyl lactate; Carboxylic acid esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate,
3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate, etc. Other esters; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN) and cyclohexanone (CHN); N,N-dimethylformamide , N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone and other amides; γ-lactone and other lactones, but are not particularly limited thereto. These solvents may be used alone or in combination of two or more.

The solvent used in this embodiment is preferably a safe solvent, more preferably P
At least one selected from GMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate, more preferably P
It is at least one selected from GMEA, PGME and CHN.

In the present embodiment, the amount of the solid component and the amount of the solvent are not particularly limited.
It is preferably 9% by mass, more preferably 1 to 50% by mass of solid components and 50 to 50% by mass of the solvent.
99% by mass, more preferably 2 to 40% by mass of solids and 60 to 98% by mass of solvent, particularly preferably 2 to 10% by mass of solids and 90 to 98% by mass of solvent.

The composition (resist composition) of the present embodiment includes, as other solid components, an acid generator (C), an acid cross-linking agent (G), an acid diffusion controller (E), and a group consisting of other components (F). It may further contain at least one selected from the above. In addition, in this specification, a "solid component" means components other than a solvent.

Here, acid generator (C), acid cross-linking agent (G), acid diffusion controller (E) and other components (F
) can be used for known ones, and is not particularly limited, but for example, International Publication No. 2013
/024778 are preferred.

[Ratio of each component]
In the resist composition of the present embodiment, the content of the compound and/or resin used as the resist base material is not particularly limited, but the total mass of solid components (resist base material, acid generator (C)
, acid cross-linking agent (G), acid diffusion control agent (E) and other components (F), and the like. ) is preferably 50 to 99.4% by mass,
More preferably 55 to 90% by mass, still more preferably 60 to 80% by mass, particularly preferably 60 to 70% by mass. When the content of the compound and/or resin used as the resist base material is within the above range, the resolution tends to be further improved and the line edge roughness (LER) tends to be further reduced.
In addition, when containing both a compound and resin as a resist base material, the said content is the total amount of both components.

[Other components (F)]
The resist composition of the present embodiment may optionally contain a resist base material, an acid generator (C), an acid cross-linking agent (G), and an acid diffusion control agent (E) to the extent that the object of the present invention is not hindered. As other components, dissolution accelerators, dissolution control agents, sensitizers, surfactants, organic carboxylic acids or phosphorus oxo acids or derivatives thereof, heat and/or photocuring catalysts, polymerization inhibitors, flame retardants, fillers , coupling agents, thermosetting resins, photosetting resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, coloring agents, nonionic surfactants, etc. Various additives can be added singly or in combination of two or more. In this specification, other components (F
) is sometimes referred to as an optional component (F).

In the resist composition of the present embodiment, a resist base material (hereinafter also referred to as "component (A)"), an acid generator (C), an acid cross-linking agent (G), an acid diffusion controller (E), and optional components Content of (F) (component (A)/acid generator (C)/acid crosslinking agent (G)/acid diffusion controller (E)/optional component (F)
) is mass% based on solids,
Preferably 50-99.4/0.001-49/0.5-49/0.001-49/0
~49,
More preferably 55 to 90/1 to 40/0.5 to 40/0.01 to 10/0 to 5,
More preferably 60 to 80/3 to 30/1 to 30/0.01 to 5/0 to 1,
Especially preferred is 60-70/10-25/2-20/0.01-3/0.
The blending ratio of each component is selected from each range so that the sum total is 100% by mass. When the blending ratio of each component is within the above range, performances such as sensitivity, resolution and developability tend to be excellent.

The resist composition of the present embodiment is usually prepared by dissolving each component in a solvent at the time of use to form a uniform solution, and then, if necessary, filtering through a filter having a pore size of about 0.2 μm. be.

The resist composition of the present embodiment can contain resins other than the resin of the present embodiment within a range that does not impede the object of the present invention. Other resins are not particularly limited. Polymers containing or derivatives thereof may be mentioned. The content of other resins is not particularly limited, and is appropriately adjusted depending on the type of component (A) used,
It is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 0 parts by mass based on 100 parts by mass of component (A).

[Physical properties of resist composition]
An amorphous film can be formed by spin coating using the resist composition of the present embodiment. Moreover, the resist composition of the present embodiment can be applied to general semiconductor manufacturing processes. Either a positive resist pattern or a negative resist pattern can be formed depending on the compound represented by the above formula (1) and/or formula (2), the type of resin obtained by using these as monomers, and/or the type of developer used. can be made separately.

In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin coating the resist composition of the present embodiment in a developer at 23° C. is preferably 5 Å/sec or less, and is preferably 0.05 to 5 Å/sec. more preferably sec, 0.0005 ~
More preferably, it is 5 Å/sec. If the dissolution rate is 5 Å/sec or less, it tends to be insoluble in a developer and easy to form into a resist. Moreover, the dissolution rate is 0.00
When it is 05 Å/sec or more, the resolution may be improved. This is due to changes in the solubility of the compounds represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent before and after exposure to light. It is presumed that this is because the contrast at the interface with the undissolved unexposed portion increases. In addition, effects of reducing LER and reducing defects are also observed.

In the case of a negative resist pattern, the dissolution rate in a developer at 23° C. of an amorphous film formed by spin-coating the resist composition of this embodiment is preferably 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble in a developer and is suitable for resist. Also, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be due to the fact that the compounds represented by formulas (1) and (2) above and/or the microscopic surface sites of the resin containing the compounds as constituents are dissolved to reduce the LER. In addition, an effect of reducing defects is also observed.

The dissolution rate can be determined by immersing an amorphous film in a developer at 23° C. for a predetermined period of time and measuring the film thickness before and after the immersion by visual observation, an ellipsometer, a QCM method, or other known methods.

In the case of a positive resist pattern, the portion of the amorphous film formed by spin-coating the resist composition of the present embodiment exposed to radiation such as KrF excimer laser, extreme ultraviolet ray, electron beam or X-ray is exposed to a developer at 23 ° C. The dissolution rate is preferably 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble in a developer and is suitable for resist. Also, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be due to the fact that the compounds represented by formulas (1) and (2) above and/or the microscopic surface sites of the resin containing the compounds as constituents are dissolved to reduce the LER. In addition, an effect of reducing defects is also observed.

In the case of a negative resist pattern, the portion of the amorphous film formed by spin-coating the resist composition of the present embodiment exposed to radiation such as KrF excimer laser, extreme ultraviolet ray, electron beam or X-ray is exposed to a developer at 23 ° C. The dissolution rate is preferably 5 Å/sec or less, more preferably 0.05 to 5 Å/sec, and 0.0005 to
More preferably, it is 5 Å/sec. If the dissolution rate is 5 Å/sec or less, it tends to be insoluble in a developer and easy to form into a resist. Moreover, the dissolution rate is 0.00
When it is 05 Å/sec or more, the resolution may be improved. This is due to changes in the solubility of the compounds represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent before and after exposure to light. It is presumed that this is because the contrast at the interface with the exposed portion that does not dissolve in the ions increases. In addition, effects of reducing LER and reducing defects are also observed.

[Film-forming composition for lithography for non-chemically amplified resist applications]
Film-forming composition for lithography for non-chemically amplified resist applications of the present embodiment (hereinafter referred to as "
Also referred to as "radiation-sensitive composition". ) is used in combination with the diazonaphthoquinone photoactive compound (B) described later, and is irradiated with g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet ray, electron beam or X-ray. It is useful as a base material for a positive resist that becomes a compound that is readily soluble in a developer upon irradiation. The properties of component (A) do not change significantly when exposed to g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet rays, electron beams, or X-rays, but diazonaphthoquinone, which is sparingly soluble in a developer, is photoactive. Since the compound (B) changes into a readily soluble compound, it becomes possible to form a resist pattern by the development process.

Since the component (A) contained in the radiation-sensitive composition of the present embodiment is a compound with a relatively low molecular weight, the roughness of the obtained resist pattern is very small. In addition, the above formula (1
), at least one selected from the group ^consisting of ^{R 0} to R ⁵ is preferably an iodine atom-containing group ^. At least one selected is preferably a group containing an iodine atom. When the component (A) having a group containing an iodine atom is applied to the radiation-sensitive composition of the present embodiment, electron beams, extreme ultraviolet rays (E
UV), X-rays and other radiation can be increased, and as a result, sensitivity can be enhanced.

The glass transition temperature of component (A) contained in the radiation-sensitive composition of the present embodiment is preferably 100°C or higher, more preferably 120°C or higher, still more preferably 140°C or higher, and particularly preferably 150°C or higher. . Although the upper limit of the glass transition temperature of component (A) is not particularly limited, it is, for example, 400°C. When the glass transition temperature of the component (A) is within the above range, it tends to have heat resistance capable of maintaining the pattern shape in the semiconductor lithography process and improve performance such as high resolution.

The amount of heat generated by crystallization of the component (A) contained in the radiation-sensitive composition of the present embodiment, determined by differential scanning calorimetric analysis of the glass transition temperature, is preferably less than 20 J/g. In addition, (crystallization temperature) - (glass transition temperature) is preferably 70°C or higher, more preferably 80°C or higher, still more preferably 100°C or higher, and particularly preferably 130°C or higher. Crystallization calorific value is 20
Less than J/g, or when (crystallization temperature) - (glass transition temperature) is within the above range, it is easy to form an amorphous film by spin-coating the radiation-sensitive composition, and the film formation required for the resist. It tends to be possible to maintain the properties for a long period of time and to improve the resolution.

In the present embodiment, the heat value of crystallization, the crystallization temperature and the glass transition temperature can be determined by differential scanning calorimetry using DSC/TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is placed in a non-sealed aluminum container and heated to above the melting point at a heating rate of 20° C./min in a nitrogen gas stream (50 mL/min). After quenching, the temperature is again raised to the melting point or higher at a heating rate of 20° C./min in a nitrogen gas stream (30 mL/min). After further quenching, again in the nitrogen gas stream (30m
L/min) The temperature is raised to 400°C at a temperature elevation rate of 20°C/min. The glass transition temperature (Tg) is defined as the temperature at the midpoint of the stepped change in the baseline (where the specific heat is halved), and the temperature of the exothermic peak that appears after that is defined as 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.

Component (A) to be contained in the radiation-sensitive composition of the present embodiment has a temperature of 100° C. or less, preferably 120° C. or less, more preferably 130° C. or less, even more preferably 140° C. or less, and particularly preferably 150° C. or less under normal pressure. WHEREIN: It is preferable that sublimability is low. Low sublimation means
In a thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, and particularly preferably 0.1%.
% or less. Due to the low sublimability, it is possible to prevent contamination of the exposure apparatus due to outgassing during exposure. Also, a good pattern shape with low roughness can be obtained.

Component (A) to be contained in the radiation-sensitive composition of the present embodiment includes propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (
PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate and having the highest dissolving power for component (A) at 23° C., preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. Particularly preferably, it is selected from the group consisting of PGMEA, PGME, and CHN, and (A) a solvent exhibiting the highest dissolving ability for the resist substrate at 23 ° C., 20% by mass or more, particularly preferably PGMEA In contrast, at 23° C., 20% by mass or more dissolves. Satisfying the above conditions facilitates use in semiconductor manufacturing processes in actual production.

[Diazonaphthoquinone photoactive compound (B)]
The diazonaphthoquinone photoactive compound (B) to be contained in the radiation-sensitive composition of the present embodiment is a diazonaphthoquinone substance including polymeric and non-polymeric diazonaphthoquinone photoactive compounds, and is generally used in positive resist compositions. There is no particular limitation as long as it is used as a photosensitive component (photosensitizer), and one or more of them can be arbitrarily selected and used.

Component (B) includes compounds obtained by reacting naphthoquinonediazide sulfonyl chloride, benzoquinonediazide sulfonyl chloride, etc. with a low-molecular-weight compound or high-molecular-weight compound having a functional group capable of condensation reaction with these acid chlorides. preferable. Here, the functional group capable of condensing with the acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, with the hydroxyl group being particularly preferred. The compound that can be condensed with an acid chloride containing a hydroxyl group is not particularly limited, and examples thereof include hydroquinone, resorcinol, 2,4-
dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6
-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,
Hydroxybenzophenones such as 3,4,4′-tetrahydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′,3,4,6′-pentahydroxybenzophenone; bis(2, 4-dihydroxyphenyl)methane, bis(2,3
, 4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane and other hydroxyphenylalkanes; 4,4′,3″,4″-tetrahydroxy-3,
hydroxytriphenylmethane such as 5,3′,5′-tetramethyltriphenylmethane, 4,4′,2″,3″,4″-pentahydroxy-3,5,3′,5′-tetramethyltriphenylmethane; Phenylmethanes and the like can be mentioned.
Further, as acid chlorides such as naphthoquinonediazide sulfonyl chloride and benzoquinonediazide sulfonyl chloride, for example, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride and the like are preferable. mentioned.

The radiation-sensitive composition of the present embodiment is prepared, for example, by dissolving each component in a solvent at the time of use to form a uniform solution, and then, if necessary, filtering through a filter having a pore size of about 0.2 μm. preferably.

[Characteristics of Radiation-Sensitive Composition]
An amorphous film can be formed by spin coating using the radiation-sensitive composition of the present embodiment. Moreover, the radiation-sensitive composition of the present embodiment can be applied to general semiconductor manufacturing processes. Either a positive resist pattern or a negative resist pattern can be produced depending on the type of developer used.

In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment in a developer at 23° C. is preferably 5 Å/sec or less, and is preferably 0.05 to 0.05 Å/sec. 5 Å/sec is more preferable, and 0.0005
More preferably, it is ~5 Å/sec. When the dissolution rate is 5 Å/sec or less,
It is insoluble in a developer and tends to be easily formed into a resist. Moreover, the dissolution rate is 0.0
When it is 005 Å/sec or more, the resolution may be improved. This is the above equation (1)
and (2) and/or the interface between the exposed area that dissolves in the developer and the unexposed area that does not dissolve in the developer due to changes in the solubility of the compound represented by (2) and/or the resin containing the compound before and after exposure to light. It is presumed that this is because the contrast of . In addition, effects of reducing LER and reducing defects are also observed.

In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment in a developer at 23° C. is preferably 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble in a developer and is suitable for a resist. Also, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be due to the fact that the compounds represented by formulas (1) and (2) above and/or the microscopic surface sites of the resin containing the compounds as constituents are dissolved to reduce the LER. In addition, an effect of reducing defects is also observed.

The dissolution rate can be determined by immersing an amorphous film in a developer at 23° C. for a predetermined time, and measuring the film thickness before and after the immersion visually, by an ellipsometer, or by a known method such as the QCM method. .

In the case of a positive resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet rays, electron beams or X-rays, or after 20 to The dissolution rate of the exposed portion after heating at 500° C. in the developer at 23° C. is preferably 10 Å/sec or more, and 10 to 10000 Å/sec.
sec is more preferred, and 100 to 1000 Å/sec is even more preferred. Dissolution rate of 10
When it is Å/sec or more, it is readily soluble in a developer and suitable for a resist. Also, when the dissolution rate is 10000 Å/sec or less, the resolution may be improved. This is the same as the above formula (
It is presumed that the microscopic surface sites of the compounds represented by 1) and (2) and/or the resin containing the compounds as constituents are dissolved to reduce the LER. In addition, an effect of reducing defects is also observed.

In the case of a negative resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet rays, electron beams or X-rays, or after 20 to The dissolution rate of the exposed portion in the developer at 23° C. after heating at 500° C. is preferably 5 Å/sec or less, and 0.05 to 5
Å/sec is more preferred, and 0.0005 to 5 Å/sec is even more preferred. If the dissolution rate is 5 Å/sec or less, it tends to be insoluble in a developer and easy to form into a resist. Further, when the dissolution rate is 0.0005 Å/sec or more,
Resolution may improve. This is a compound represented by the above formulas (1) and (2) and /
Alternatively, it is presumed that the contrast at the interface between the unexposed area that dissolves in the developer and the exposed area that does not dissolve in the developer increases due to changes in the solubility of the resin containing the compound as a constituent before and after exposure. In addition, effects of reducing LER and reducing defects are also observed.

[Ratio of each component]
In the radiation-sensitive composition of the present embodiment, the content of component (A) is the total weight of solid components (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc., which are optionally used). is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25
~75% by mass. When the content of the component (A) is within the above range, the radiation-sensitive composition of the present embodiment tends to be able to obtain a pattern with high sensitivity and low roughness.

In the radiation-sensitive composition of the present embodiment, the content of the diazonaphthoquinone photoactive compound (B) is the total weight of solid components (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc.). The sum of optionally used solid components, hereinafter the same), preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90
% by weight, particularly preferably 25 to 75% by weight. The radiation-sensitive composition of the present embodiment is
When the content of the diazonaphthoquinone photoactive compound (B) is within the above range, it tends to be possible to obtain a pattern with high sensitivity and low roughness.

[Other components (D)]
The radiation-sensitive composition of the present embodiment may optionally contain, as components other than the component (A) and the diazonaphthoquinone photoactive compound (B), an acid generator, as long as the object of the present invention is not hindered.
acid cross-linking agent, acid diffusion controller, dissolution accelerator, dissolution controller, sensitizer, surfactant, organic carboxylic acid or phosphorus oxoacid or derivative thereof, heat and/or photocuring catalyst, polymerization inhibitor, flame Repellents, fillers, coupling agents, thermosetting resins, photo-setting resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, coloring agents, nonionic interfaces One or more of various additives such as activators can be added. In addition, in this specification, another component (D) may be called an arbitrary component (D).

In the radiation-sensitive composition of the present embodiment, the blending ratio of each component (component (A)/diazonaphthoquinone photoactive compound (B)/optional component (D)) is mass % based on solid components,
preferably 1 to 99/99 to 1/0 to 98,
more preferably 5 to 95/95 to 5/0 to 49,
More preferably 10 to 90/90 to 10/0 to 10,
Even more preferably 20 to 80/80 to 20/0 to 5,
Especially preferred is 25-75/75-25/0.
The blending ratio of each component is selected from each range so that the sum total is 100% by mass. When the blending ratio of each component of the radiation-sensitive composition of the present embodiment is within the above range, in addition to roughness,
They tend to be excellent in performance such as sensitivity and resolution.

The radiation-sensitive composition of the present embodiment may contain other resins as long as the object of the present invention is not impaired. Such other resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units, or Derivatives of these and the like are included. The blending amount of these resins is appropriately adjusted according to the type of component (A) used, but it is preferably 30 parts by mass or less, more preferably 10 parts by mass per 100 parts by mass of component (A). It is not more than 5 parts by mass, more preferably not more than 5 parts by mass, and particularly preferably 0 part by mass.

[Method of forming a resist pattern]
The method for forming a resist pattern in the present embodiment comprises forming a photoresist layer on a substrate using the resist composition or the radiation-sensitive composition of the present embodiment described above, and then applying radiation to a predetermined region of the photoresist layer. and developing. More specifically, a step of forming a resist film on a substrate using the resist composition or the radiation-sensitive composition of the present embodiment described above, a step of exposing the formed resist film, and a step of developing the resist film. and forming a resist pattern. The resist pattern in this embodiment can also be formed as an upper layer resist in a multilayer process.

The method for forming the resist pattern is not particularly limited, but includes, for example, the following methods. First, a resist film is formed by coating a conventionally known substrate with a resist composition or a radiation-sensitive composition by a coating means such as spin coating, casting coating, or roll coating. Conventionally known substrates are not particularly limited, and examples thereof include substrates for electronic components and substrates having predetermined wiring patterns formed thereon. More specifically, silicon wafers,
Substrates made of metals such as copper, chromium, iron and aluminum, glass substrates, and the like are included. Materials for the wiring pattern include, for example, copper, aluminum, nickel, and gold. In addition, if necessary, an inorganic and/or organic film may be provided on the substrate. Inorganic films include inorganic antireflection coatings (inorganic BARC). Organic films include organic antireflection coatings (organic BARC). The substrate may be surface-treated with hexamethylenedisilazane or the like.

Next, if necessary, the substrate coated with the resist composition or radiation-sensitive composition is heated. The heating conditions vary depending on the formulation composition of the resist composition or the radiation-sensitive composition, but range from 20 to
It is preferably 250°C, more preferably 20 to 150°C. Heating is preferable because it tends to improve the adhesion of the resist to the substrate. Next, the resist film is exposed in a desired pattern to radiation selected from the group consisting of visible light, ultraviolet rays, excimer lasers, electron beams, extreme ultraviolet rays (EUV), X-rays, and ion beams. Exposure conditions and the like are appropriately selected according to the composition of the resist composition or the radiation-sensitive composition. In this embodiment, in order to stably form a fine pattern with high precision in exposure, it is preferable to heat after radiation irradiation. The heating conditions are preferably 20 to 250.degree. C., more preferably 20 to 150.degree.

Next, a predetermined resist pattern is formed by developing the exposed resist film with a developer. As the developer, the solubility parameter (SP value ), and polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, or alkaline aqueous solutions can be used.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2
-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol , acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3 -ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate,
and propyl lactate.

Examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n
-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-
Alcohols such as octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether and diethylene glycol monomethyl Glycol ether solvents such as ether, triethylene glycol monoethyl ether, methoxymethylbutanol, and the like are included.

Examples of ether solvents include the above glycol ether solvents, dioxane,
tetrahydrofuran and the like.

Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, 1,
3-dimethyl-2-imidazolidinone and the like.

Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

A plurality of the above solvents may be mixed, or a solvent other than the above or water may be mixed and used within the range of performance. However, from the viewpoint of sufficiently exhibiting the effects of the present invention, the water content of the developer as a whole is preferably less than 70% by mass, more preferably less than 50% by mass, and less than 30% by mass. More preferably, it is less than 10% by mass, and particularly preferably contains substantially no water. That is, the content of the organic solvent in the developer is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, relative to the total amount of the developer.
It is more preferably 70% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

Examples of alkaline aqueous solutions include mono-, di- or trialkylamines, mono-
, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and alkaline compounds such as choline.

In particular, the developer is at least selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents from the viewpoint of improving the resist performance such as the resolution and roughness of the resist pattern. Developers containing one solvent are preferred.

The vapor pressure of the developer at 20° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less. When the vapor pressure of the developer is 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed,
The temperature uniformity within the wafer plane is improved, and as a result, the dimensional uniformity within the wafer plane tends to be improved.

Examples of specific developers having a vapor pressure of 5 kPa or less at 20° C. include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl Ketone solvents such as cyclohexanone, phenylacetone, and methyl isobutyl ketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropyl pionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate,
Ester solvents such as ethyl lactate, butyl lactate and propyl lactate; n-propyl alcohol,
isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert
-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2
-Alcohol solvents such as pentanol, n-heptyl alcohol, n-octyl alcohol and n-decanol; Glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; Ethylene glycol monomethyl ether, propylene glycol monomethyl ether and ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol ether solvents such as methoxymethylbutanol; ether solvents such as tetrahydrofuran; N-methyl-2-pyrrolidone, N,N-dimethyl Amide solvents such as acetamide and N,N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene; and aliphatic hydrocarbon solvents such as octane and decane.

Examples of specific developers having a vapor pressure of 2 kPa or less at 20° C. include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl Ketone solvents such as cyclohexanone and phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3 -Methoxybutyl acetate, 3-methyl-
Ester solvents such as 3-methoxybutyl acetate, ethyl lactate, butyl lactate, and propyl lactate; n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pen Tanol, n
-Alcoholic solvents such as heptyl alcohol, n-octyl alcohol and n-decanol; Glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol Glycol ether solvents such as monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethylbutanol; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide , xylene; and aliphatic hydrocarbon solvents such as octane and decane.

An appropriate amount of surfactant can be added to the developer if necessary. Although the surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used. Examples of these fluorine and/or silicon-based surfactants include, for example, JP-A-62-36663, JP-A-61-226746,
JP-A-61-226745, JP-A-62-170950, JP-A-63-34
540, JP-A-7-230165, JP-A-8-62834, JP-A-9
-54432, JP-A-9-5988, US Pat. No. 5,405,720,
5360692, 5529881, 5296330, 5436098, 5576143, 5294511, 5
824451, preferably non-ionic surfactants. Nonionic surfactants are not particularly limited, but fluorine-based surfactants or silicon-based surfactants are preferred.

The amount of surfactant used is generally 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, relative to the total amount of the developer.

As a development method, for example, a method of immersing the substrate in a tank filled with a developer for a certain period of time (
(dip method), a method in which the developer is piled up on the substrate surface by surface tension and is developed by standing still for a certain period of time (paddle method), a method in which the developer is sprayed onto the substrate surface (spray method), rotating at a constant speed. A method (dynamic dispensing method) or the like can be applied in which the developer is continuously applied onto the substrate while the developer application nozzle is scanned at a constant speed. The time for pattern development is not particularly limited, but is preferably 10 to 90 seconds.

Further, after the step of developing, a step of stopping development may be performed while replacing the solvent with another solvent.

After development, it is preferable to include a step of washing with a rinse containing an organic solvent.

The rinsing liquid used in the rinsing step after development is not particularly limited as long as it does not dissolve the resist pattern cured by crosslinking, and a common solution containing an organic solvent or water can be used. As the rinse solution, it is preferable to use a rinse solution containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. . More preferably, after development, a step of washing with a rinsing solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents is performed. More preferably, after development, a step of washing with a rinse solution containing an alcohol-based solvent or an ester-based solvent is performed. Even more preferably, after development, a step of washing with a rinse containing a monohydric alcohol is performed. Particularly preferably, after development, a step of washing with a rinsing solution containing a monohydric alcohol having 5 or more carbon atoms is performed. The time for pattern rinsing is not particularly limited, but is preferably 10 to 90 seconds.

Here, the monohydric alcohol used in the rinsing step after development includes linear, branched,
Cyclic monohydric alcohols include, specifically, 1-butanol, 2-butanol, 3-
methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferred monohydric alcohols having 5 or more carbon atoms are 1-hexanol and 2-hexanol. , 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like.

A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Moisture content in the rinse liquid is 10% by mass
By doing the following, there is a tendency that better development characteristics can be obtained.

The vapor pressure of the rinse used after development is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20°C.
It is more preferably 0.12 kPa or more and 3 kPa or less. Vapor pressure of rinse liquid is 0
. When the pressure is 05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, swelling due to penetration of the rinse liquid is further suppressed, and the dimensional uniformity in the wafer surface tends to be further improved. be.

An appropriate amount of surfactant may be added to the rinse solution before use.

In the rinsing step, the developed wafer is washed with the rinsing liquid containing the above organic solvent. The method of the cleaning treatment is not particularly limited, but for example, a method of continuously applying the rinse solution onto the substrate rotating at a constant speed (rotation coating method), or immersing the substrate in a tank filled with the rinse solution for a certain period of time. A method (dip method), a method of spraying a rinse solution onto the substrate surface (spray method), etc. can be applied. It is preferable to remove the rinsing liquid from the substrate.

A patterned wiring board is obtained by etching after forming a resist pattern. Etching can be performed by known methods such as dry etching using plasma gas and wet etching with alkaline solution, cupric chloride solution, ferric chloride solution or the like.

Plating can also be performed after forming the resist pattern. Examples of plating methods include copper plating, solder plating, nickel plating, and gold plating.

Residual resist patterns after etching can be removed with an organic solvent. As an organic solvent, PGMEA (propylene glycol monomethyl ether acetate), PGME
(propylene glycol monomethyl ether), EL (ethyl lactate) and the like. Examples of the peeling method include an immersion method and a spray method. Moreover, the wiring board on which the resist pattern is formed may be a multilayer wiring board and may have a small-diameter through hole.

The wiring board in this embodiment can also be formed by a method of vapor-depositing a metal in a vacuum after forming a resist pattern, and then dissolving the resist pattern with a solution, that is, a lift-off method.

[Film-forming composition for lithography for underlayer film applications]
The film-forming composition for lithography for underlayer film applications (hereinafter also referred to as "underlayer film-forming material") in the present embodiment includes the compound represented by the above formula (0) and the compound represented by the above formula (0). The resin obtained as a monomer, more specifically the compound represented by the above formula (1), the resin obtained by using the compound represented by the above formula (1) as a monomer, the compound represented by the formula (2) and the formula ( It contains at least one substance selected from the group consisting of resins obtained by using the compound represented by 2) as a monomer. In the present embodiment, from the viewpoint of coatability and quality stability, the above-mentioned substance is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, more preferably 50 to 100% by mass, in the underlayer film-forming material. %, and particularly preferably 100% by mass.

The underlayer film forming material of the present embodiment can be applied to a wet process and has excellent heat resistance and etching resistance. Furthermore, since the underlayer film-forming material of the present embodiment uses the above substances, deterioration of the film during high-temperature baking is suppressed, and an underlayer film having excellent etching resistance to oxygen plasma etching or the like can be formed. . Furthermore, since the underlayer film-forming material of the present embodiment has excellent adhesion to the resist layer, an excellent resist pattern can be obtained.
The underlayer film-forming material of the present embodiment may contain a known underlayer film-forming material for lithography, etc., as long as the effects of the present invention are not impaired.

[solvent]
The underlayer film-forming material in this embodiment may contain a solvent. As the solvent used for the underlayer film-forming material, any known solvent can be appropriately used as long as it dissolves at least the above-mentioned substances.

Specific examples of the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate and methyl acetate. , Ester solvents such as ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol, 1-ethoxy-2-propanol; toluene, xylene , aromatic hydrocarbons such as anisole. These solvents can be used singly or in combination of two or more.

Among the above solvents, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, and anisole are particularly preferred from the viewpoint of safety.

The content of the solvent is not particularly limited, but from the viewpoint of solubility and film formation, it is preferably 100 to 10,000 parts by mass, and 200 to 10,000 parts by mass with respect to 100 parts by mass of the lower layer film-forming material.
It is more preferably 5000 parts by mass, and even more preferably 200 to 1000 parts by mass.

[Crosslinking agent]
From the viewpoint of suppressing intermixing, etc., the underlayer film forming material in the present embodiment is
A cross-linking agent may be contained as necessary. Although the cross-linking agent is not particularly limited, for example, those described in International Publication No. 2013/024779 can be used.

The content of the cross-linking agent in the underlayer film forming material is not particularly limited, but is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the underlayer film forming material. . By setting the content of the cross-linking agent within the above range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect is enhanced, and the film formability after cross-linking tends to be enhanced. .

[Acid generator]
The underlayer film-forming material in the present embodiment may contain an acid generator, if necessary, from the viewpoint of further accelerating the cross-linking reaction by heat. As acid generators, those that generate acid by thermal decomposition, those that generate acid by light irradiation, and the like are known, and any of them can be used. As the acid generator, for example, those described in International Publication No. 2013/024779 can be used.

Although the content of the acid generator in the underlayer film-forming material is not particularly limited, the underlayer film-forming material 100
It is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 4 parts by mass.
It is 0 parts by mass. By setting the content of the acid generator within the above range, the amount of acid generated tends to increase and the cross-linking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.

[Basic compound]
The underlayer film-forming material in the present embodiment may contain a basic compound from the viewpoint of improving storage stability.

The basic compound plays a role of a quencher for the acid to prevent the slight amount of acid generated from the acid generator from proceeding with the cross-linking reaction. Examples of such a basic compound include, but are not particularly limited to, those described in International Publication No. 2013/024779.

The content of the basic compound in the underlayer film-forming material is not particularly limited, but underlayer film-forming material 1
It is preferably 0.001 to 2 parts by mass, more preferably 0.001 to 2 parts by mass with respect to 00 parts by mass.
01 to 1 part by mass. By setting the content of the basic compound within the above range, the storage stability tends to be enhanced without excessively impairing the cross-linking reaction.

[Other additives]
Further, the underlayer film-forming material in the present embodiment may contain other resins and/or compounds for the purpose of imparting heat or light curability and controlling absorbance. Such other resins and/or compounds include naphthol resins, xylene resin naphthol-modified resins,
Phenol-modified naphthalene resin; polyhydroxystyrene, dicyclopentadiene resin, (meth)acrylate, dimethacrylate, trimethacrylate, tetramethacrylate, naphthalene rings such as vinylnaphthalene and polyacenaphthylene, biphenyl rings such as phenanthrenequinone and fluorene , thiophene, resins containing heterocycles having heteroatoms such as indene, and resins not containing aromatic rings; Examples include resins or compounds containing an alicyclic structure, but are not particularly limited thereto. Furthermore, the underlayer film-forming material in the present embodiment may contain known additives. Examples of known additives include, but are not limited to, heat and/or photo-curing catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photo-curing resins, dyes, and pigments. , thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, coloring agents, nonionic surfactants and the like.

[Method for forming underlayer film for lithography and multilayer resist pattern]
The underlayer film for lithography in this embodiment is formed from the underlayer film-forming material described above.

Further, in the resist pattern forming method of the present embodiment, an underlayer film is formed on a substrate using the above composition, at least one photoresist layer is formed on the underlayer film, and then the photoresist layer is formed. It includes a step of irradiating a predetermined area with radiation and performing development. More specifically, the step (A-1) of forming an underlayer film on a substrate using the underlayer film-forming material of the present embodiment, and the step of forming at least one photoresist layer on the underlayer film ( A-2) and the above (A
-2) After the step (A-3), a predetermined region of the photoresist layer is irradiated with radiation and developed.

Further, the circuit pattern forming method of the present embodiment comprises forming an underlayer film on a substrate using the composition, forming an intermediate layer film on the underlayer film using a resist intermediate layer film material, and forming the intermediate layer film on the underlayer film. forming at least one photoresist layer on the film;
A step of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern;
The intermediate layer film is etched using the resist pattern as a mask, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask. The step of forming a pattern is included.

More specifically, a step (B-1) of forming an underlayer film on a substrate using the underlayer film forming material of the present embodiment, and a resist intermediate layer film material containing silicon atoms is used on the underlayer film. forming an intermediate layer film (B-2), forming at least one photoresist layer on the intermediate layer film (B-3), and after the step (B-3), A step (B-4) of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern, and after the step (B-4), using the resist pattern as a mask, the intermediate layer film is etched, the underlayer film is etched using the resulting intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained underlayer film pattern as an etching mask to form a pattern on the substrate (B-5). including.

As long as the underlayer film for lithography in this embodiment is formed from the underlayer film-forming material of this embodiment, the formation method is not particularly limited, and known techniques can be applied. For example, after the underlayer film material of the present embodiment is applied onto a substrate by a known coating method such as spin coating or screen printing or a printing method, the organic solvent is removed by volatilization or the like to form the underlayer film. can do.

When forming the lower layer film, it is preferable to perform baking in order to suppress the occurrence of the mixing phenomenon with the upper layer resist and promote the cross-linking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450° C., more preferably 200° C.
~400°C. Also, the baking time is not particularly limited, but it is preferably in the range of 10 to 300 seconds. The thickness of the underlayer film can be appropriately selected according to the required performance, and is not particularly limited, but is generally preferably about 30 to 20000 nm, more preferably 50 to 15000 nm.

After forming the underlayer film, in the case of a two-layer process, a silicon-containing resist layer or a single-layer resist made of ordinary hydrocarbons is placed thereon, and in the case of a three-layer process, a silicon-containing intermediate layer is placed thereon, and further thereon a silicon-containing intermediate layer. It is preferable to fabricate a single-layer resist layer that does not contain silicon. In this case, a known photoresist material can be used for forming this resist layer.

After forming the underlayer film on the substrate, in the case of a two-layer process, a silicon-containing resist layer or a conventional hydrocarbon monolayer resist can be formed on the underlayer film. In the case of a three-layer process, a silicon-containing intermediate layer can be formed on the underlayer film, and a silicon-free monolayer resist layer can be formed on the silicon-containing intermediate layer. In these cases, the photoresist material for forming the resist layer can be appropriately selected from known materials and used, and is not particularly limited.

As a silicon-containing resist material for a two-layer process, from the viewpoint of oxygen gas etching resistance, a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as a base polymer, and an organic solvent, an acid generator, A positive photoresist material containing a basic compound or the like, if necessary, is preferably used. Here, as the silicon atom-containing polymer, a known polymer used in this type of resist material can be used.

Polysilsesquioxane-based intermediate layers are preferably used as silicon-containing intermediate layers for three-layer processes. Reflection tends to be effectively suppressed by providing the intermediate layer with the effect of an antireflection film. For example, in the process for 193 nm exposure,
When a material containing many aromatic groups and having high substrate etching resistance is used as the lower layer film, the k value tends to increase and the substrate reflection tends to increase. % or less. As an intermediate layer having such an antireflection effect,
Although not limited to the following, for 193 nm exposure, acid- or heat-crosslinkable polysilsesquioxane into which a phenyl group or a light-absorbing group having a silicon-silicon bond is introduced is preferably used.

An intermediate layer formed by a chemical vapor deposition (CVD) method can also be used. Although not limited to the following, for example, a SiON film is known as an intermediate layer that is produced by a CVD method and is highly effective as an antireflection film. In general, forming an intermediate layer by a wet process such as a spin coating method or screen printing is simpler and more cost effective than a CVD method. The upper layer resist in the three-layer process may be either positive type or negative type, and may be the same as a commonly used single layer resist.

Furthermore, the underlayer film in this embodiment can also be used as an antireflection film for a normal single-layer resist or as a base material for suppressing pattern collapse. Since the underlayer film is excellent in etching resistance for underlayer processing, it can also be expected to function as a hard mask for underlayer processing.

When the resist layer is formed from the photoresist material, a wet process such as spin coating or screen printing is preferably used as in the case of forming the underlayer film. After the resist material is applied by spin coating or the like, prebaking is usually performed, and it is preferable to perform this prebaking at 80 to 180° C. for 10 to 300 seconds. Then, according to a conventional method, exposure is performed, post-exposure bake (PEB),
A resist pattern can be obtained by developing. Although the thickness of the resist film is not particularly limited, it is generally preferably 30 to 500 nm, more preferably 50 to 4 nm.
00 nm.

Also, the exposure light may be appropriately selected and used according to the photoresist material to be used. Generally, high energy rays with a wavelength of 300 nm or less, specifically 248 nm, 193 nm,
Excimer lasers of 157 nm, soft X-rays of 3 to 20 nm, electron beams, X-rays and the like can be mentioned.

In the resist pattern formed by the above-described method, pattern collapse is suppressed by the lower layer film. Therefore, by using the underlayer film of this embodiment, a finer pattern can be obtained, and the exposure dose required for obtaining the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used for etching the lower layer film in the two-layer process. As the gas etching, etching using oxygen gas is suitable. In addition to oxygen gas, He, Ar
It is also possible to add inert gases such as CO, _CO2 , _NH3 , _SO2 , _N2 , _NO2 and _H2 gases. Gas etching can also be performed using _only CO, _CO2 , _NH3 , _N2 , NO2, and _H2 gases without using oxygen gas. In particular, the latter gas is preferably used for sidewall protection to prevent undercutting of pattern sidewalls.

On the other hand, gas etching is also preferably used for etching the intermediate layer in the three-layer process. As the gas etching, the same one as described in the above two-layer process can be applied. In particular, it is preferable to process the intermediate layer in the three-layer process using a freon-based gas and using a resist pattern as a mask. After that, as described above, the intermediate layer pattern is used as a mask to perform, for example, oxygen gas etching, whereby the lower layer film can be processed.

Here, when forming an inorganic hard mask intermediate layer film as the intermediate layer, CVD method or ALD method is used.
A silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) are formed by a method or the like. The method for forming the nitride film is not limited to the following, but for example, the methods described in Japanese Patent Application Laid-Open No. 2002-334869 (Patent Document 6) and WO2004/066377 (Patent Document 7) can be used. Although a photoresist film can be directly formed on such an intermediate layer film, an organic anti-reflective coating (BARC) is formed on the intermediate layer film by spin coating, and a photoresist film is formed thereon. You may

As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. Reflection tends to be effectively suppressed by imparting an antireflection film effect to the resist intermediate layer film. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following.
The one described in JP-A-2007-226204 (Patent Document 9) can be used.

Subsequent etching of the substrate can also be carried out by conventional methods, e.g.
_2. SiN can be etched mainly with flon-based gas, and p-Si, Al, and W can be etched mainly with chlorine-based or bromine-based gas. When the substrate is etched with Freon-based gas, the silicon-containing resist in the two-layer resist process and the silicon-containing intermediate layer in the three-layer process are stripped at the same time as the substrate is processed. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is removed separately, and generally, after the substrate is processed, the dry-etching removal is performed with a flon-based gas. .

The underlayer film in this embodiment is characterized by excellent etching resistance of the substrate. As the substrate, a known substrate can be appropriately selected and used, and it is not particularly limited, but examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. be done. The substrate may also be a laminate having a film to be processed (substrate to be processed) on a base material (support). Such films to be processed include Si, SiO ₂ , SiON, SiN, pS
Various Low-k films such as i, α-Si, W, W-Si, Al, Cu, and Al-Si, and their stopper films, etc., usually made of a material different from that of the substrate (support) is used.
The thickness of the substrate to be processed or the film to be processed is not particularly limited.
It is preferably about 10000 nm, more preferably 75 to 5000 nm.

Hereinafter, the present embodiment will be described in more detail with reference to Synthesis Examples, Synthesis Examples, Examples, and Comparative Examples, but the present embodiment is not limited by these examples.

(Carbon concentration and oxygen concentration)
Carbon concentration and oxygen concentration (% by mass) were measured by organic elemental analysis using the following equipment.
Apparatus: CHN coder MT-6 (manufactured by Yanako Analysis Industry Co., Ltd.)

(molecular weight)
The molecular weight of the compound was determined by Water's Acquity UPLC/MALDI-Syna
Measured by LC-MS analysis using pt HDMS.
In addition, gel permeation chromatography (GPC) analysis was performed under the following conditions to obtain polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (Mw/Mn).
Apparatus: Shodex GPC-101 type (manufactured by Showa Denko Co., Ltd.)
Column: KF-80M x 3
Eluent: THF 1 mL/min
Temperature: 40°C

(solubility)
Dissolve the compound in propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethyl urea (TMU) at 23° C. to form a 10 wt % solution. After one week, the results were evaluated according to the following criteria.
Evaluation A: It was visually confirmed that there was no precipitate in any solvent. Evaluation C: It was visually confirmed that there was a precipitate in all solvents.

[Structure of compound]
The structure of the compound is obtained from Bruker's "Advance600II spectrum
ter” was used to perform 1H-NMR measurement under the following conditions for confirmation.
Frequency: 400MHz
Solvent: d6-DMSO
Internal standard: TMS
Measurement temperature: 23°C

<Synthesis Example 1> Synthesis of XBisN-1 3.20 g (20 mmol) of 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich) and 4-biphenylcarboxyl were added to a container having an internal volume of 100 mL equipped with a stirrer, a cooling tube and a burette. Aldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 1.82 g (10 mmol) and 30 mL
of methyl isobutyl ketone, 5 mL of 95% sulfuric acid was added, and the reaction mixture was stirred at 100° C. for 6 hours to carry out a reaction. Next, the reaction solution was concentrated, 50 g of pure water was added to precipitate a reaction product, cooled to room temperature, and separated by filtration. The obtained solid matter was filtered, dried, and then separated and purified by column chromatography to obtain 3 target compounds represented by the following formula.
. 05 g. It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.7 (2H, OH), 7.2-8.5 (19H, Ph-H), 6.6
(1H, CH)
It should be noted that the fact that the substitution position of 2,6-naphthalenediol is at the 1st position was confirmed from the fact that the signals of the protons at the 3rd and 4th positions are doublets.

（ＸＢｉｓＮ－１）

(XBisN-1)

<Synthesis Example 2> Synthesis of BisF-1 A vessel with an internal volume of 200 mL equipped with a stirrer, a condenser and a burette was prepared. In this container, 30 g (161 mmol) of 4,4-biphenol (reagent manufactured by Tokyo Kasei Co., Ltd.), 15 g (82 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 100 ml of butyl acetate
L and p-toluenesulfonic acid (reagent manufactured by Kanto Chemical Co., Ltd.) 3.9 g (21 mmol)
was added to prepare a reaction solution. This reaction solution was stirred at 90° C. for 3 hours to carry out the reaction. Next, the reaction solution was concentrated, 50 g of heptane was added to precipitate the reaction product, cooled to room temperature, and separated by filtration. After drying the solid obtained by filtration, the target compound (BisF-1) 5 represented by the following formula is obtained by separation and purification by column chromatography.
. 8 g was obtained.
The following peaks were found by 400 MHz- ¹ H-NMR, confirming the chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.4 (4H, OH), 6.8-7.8 (22H, Ph-H), 6.2
(1H, CH)
As a result of measuring the molecular weight of the obtained compound by the above method, it was 536.

（ＢｉｓＦ－１）

(BisF-1)

<Synthesis Example 3> Synthesis of Al-XBisN-1 The above formula (XBisN
-1) 9.8 g (21 mmol) of the compound represented by and 6.2 g (45 mmol) of potassium carbonate
l) was added to 100 mL of acetone, and 5.4 (45 mm) of allyl bromide
ol) g and 2.0 g of 10-crown-6 were added, and the resulting reaction mixture was stirred under reflux for 7 hours to carry out the reaction. Next, the solid content was removed from the reaction liquid by filtration, cooled in an ice bath, and the reaction liquid was concentrated to deposit a solid substance. The precipitated solid matter was filtered, dried, and then separated and purified by column chromatography to obtain the target compound represented by the following formula (Al-XBisN-1)4.
0 g was obtained.
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (Al-XBisN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2-7.8 (19H, Ph-H), 6.7 (1H, CH), 6.1
(2H, -CH=CH ₂ ), 5.4-5.5 (4H, -CH=CH ₂ )
As a result of measuring the molecular weight of the obtained compound by the above method, it was 546.

（Ａｌ－ＸＢｉｓＮ－１）

(Al-XBisN-1)

<Synthesis Example 4> Synthesis of Al-BisF-1 Synthesis Example 1 except that the compound represented by the above formula (BisF-1) was used instead of the compound represented by the above formula (XBisN-1). and the following formula (Al-Bis
3.0 g of the objective compound represented by F-1) was obtained.
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (Al-BisF-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8-7.8 (22H, Ph-H), 6.2 (1H, CH), 6.1
(4H, -CH=CH ₂ ), 5.4-5.5 (8H, -CH=CH ₂ ),
As a result of measuring the molecular weight of the obtained compound by the above method, it was 872.

（Ａｌ－ＢｉｓＦ－１）

(Al-BisF-1)

<Synthesis Example 1> Synthesis of AlOH-XBisN-1 The above formula (Al-XB
6.1 g (11 mmol) of the compound represented by isN-1) was added to 6.0 mL, the reaction solution was stirred at 130° C. for 6 hours, then heated to 160° C. and reacted for 24 hours. Next, 30 mL of water was added to the reaction solution to precipitate crystals, which were separated by filtration. The resulting solid matter was filtered, dried, and separated and purified by column chromatography to obtain 0.90 g of the target compound represented by the following formula.
It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.6 (2H, OH), 7.3-8.5 (17H, Ph-H), 6.6
(1H, CH), 5.9 (2H, -CH=CH ₂ ), 4.9 (4H, -CH=CH ₂ ),
3.8(4H, _-CH2- )
As a result of measuring the molecular weight of the obtained compound by the above method, it was 546.

（ＡｌＯＨ－ＸＢｉｓＮ－１）

(AlOH-XBisN-1)

The obtained compound had a thermal decomposition temperature of 400° C. and a glass transition temperature of 211° C., confirming high heat resistance.

<Synthesis Example 2> Synthesis of AlOH-BisF-1 The formula (Al-Bi
6.1 g (9 mmol) of the compound represented by sF-1) was added to 6.0 mL, and the reaction solution was
The mixture was stirred at 0°C for 6 hours, then heated to 160°C and reacted for 24 hours. Next, 30 mL of water was added to the reaction solution to precipitate crystals, which were separated by filtration. The resulting solid matter was filtered, dried, and separated and purified by column chromatography to obtain 1.05 g of the target compound represented by the following formula.
It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.4 (4H, OH), 6.8-7.8 (18H, Ph-H), 6.2
(1H, CH), 5.9 (4H, -CH=CH ₂ ), 4.9 (8H, -CH=CH ₂ ),
3.8(8H, _-CH2- )
As a result of measuring the molecular weight of the obtained compound by the above method, it was 696.

（ＡｌＯＨ－ＢｉｓＦ－１）

(AlOH-BisF-1)

It has a thermal decomposition temperature of 390° C. and a glass transition temperature of 200° C., confirming high heat resistance.

<Synthesis Example 5>
A 10 L four-necked flask capable of bottom extraction, equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. In this four-necked flask, 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.1 parts of a 40% by mass formalin aqueous solution were placed in a nitrogen stream.
kg (28 mol as formaldehyde, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.97 mL of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted under normal pressure at 100° C. for 7 hours while refluxing. After that, ethylbenzene (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) 1 as a dilution solvent
. 8 kg was added to the reaction liquid, and after allowing to stand still, the lower aqueous phase was removed. Furthermore, neutralization and washing with water were carried out, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of light brown solid dimethylnaphthalene formaldehyde resin.
The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn:562.

Subsequently, a four-necked flask with an internal volume of 0.5 L equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. In this four-necked flask, 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of p-toluenesulfonic acid were charged under a nitrogen stream, and the temperature was raised to 190 ° C. After heating for 1 hour, it was stirred. After that, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was raised to 220° C. and reacted for 2 hours. After dilution with the solvent, neutralization and washing were carried out, and the solvent was removed under reduced pressure to obtain 126.1 g of modified resin (CR-1) as a dark brown solid.
The resulting resin (CR-1) has Mn: 885, Mw: 2220, Mw/Mn: 4.17
Met. Also, the carbon concentration was 89.1% by mass and the oxygen concentration was 4.5% by mass.

<Examples 1 and 2, Comparative Example 1>
The solubility of each of AlOH-XBisN-1, AlOH-BisF-1 and CR-1 was evaluated. Table 1 shows the results.

In addition, underlayer film-forming materials for lithography having compositions shown in Table 1 were prepared. Next, these lithographic underlayer film-forming materials were spin-coated on a silicon substrate, and then heated at 240°C.
for 60 seconds and then at 400° C. for 120 seconds to prepare underlayer films each having a thickness of 200 nm. The following acid generators, cross-linking agents and organic solvents were used.
・Acid generator: Ditert-butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI) manufactured by Midori Chemical Co., Ltd.
・Cross-linking agent: Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
・Organic solvent: Methyl amyl ketone (MAK) manufactured by Kanto Chemical Co., Ltd.

[Etching resistance]
An etching test was performed under the conditions shown below to evaluate the etching resistance. Table 1 shows the evaluation results
shown in

[Etching test]
Etching device: RIE-10NR manufactured by Samco International
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF4 gas flow rate: _O2 gas flow rate = 50: ₅ :5 (sccm)

Etching resistance was evaluated by the following procedure.
First, instead of the compound (AlOH-XBisN-1), novolac (PS manufactured by Gun Ei Kagaku Co., Ltd.)
M4357) was used, but under the same conditions as in Example 1, a novolac underlayer film was produced. Then, the above-described etching test was performed on this novolac underlayer film, and the etching rate at that time was measured.
Next, the lower layer films of Examples 1 and 2 and Comparative Example 1 were subjected to the etching test in the same manner as described above, and the etching rate at that time was measured. Using the etching rate of the novolac underlayer film as a reference, the etching resistance was evaluated according to the following evaluation criteria.

[Evaluation criteria]
A: The etching rate is less than −10% compared to the novolac underlayer film B: The etching rate is −10% to +5% compared to the novolac underlayer film
C: The etching rate is more than +5% compared to the novolac underlayer film

<Examples 3 and 4>
Next, AlOH-XBisN-1 or AlOH-BisF obtained in Examples 1 and 2
Each solution of an underlayer film forming material for lithography containing -1 was coated on a 300 nm-thickness SiO ₂ substrate and baked at 240° C. for 60 seconds and further at 400° C. for 120 seconds to form a 70 nm-thick underlayer. A film was formed. A resist solution for ArF is applied on the underlayer film,
A photoresist layer having a film thickness of 140 nm was formed by baking at 130° C. for 60 seconds. As the ArF resist solution, a compound of the following formula (11): 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass were blended. The prepared one was used.

The compound of formula (11) is 2-methyl-2-methacryloyloxyadamantane 4.15
g, 3.00 g of methacrylloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to prepare a reaction solution. This reaction solution was
After polymerizing for 22 hours while maintaining the reaction temperature at 63° C., the reaction solution was dropped into 400 mL of n-hexane. The produced resin thus obtained was coagulated and purified, and the produced white powder was filtered and dried under reduced pressure at 40° C. overnight.

（１１）

(11)

In the above formula (11), "40", "40", and "20" indicate the ratio of each structural unit, not the block copolymer.

Then, using an electron beam lithography system (Elionix; ELS-7500, 50 keV), the photoresist layer is exposed, baked (PEB) at 115 ° C. for 90 seconds, and 2.38% by mass of tetramethylammonium hydroxide ( A positive resist pattern was obtained by developing with an aqueous TMAH) solution for 60 seconds.

The shapes and defects of the resulting resist patterns of 55 nm L/S (1:1) and 80 nm L/S (1:1) were observed using an electron microscope (S-4800, manufactured by Hitachi, Ltd.).
With respect to the shape of the resist pattern after development, a pattern with good rectangularity without pattern collapse was evaluated as "good", and other than that was evaluated as "bad". Further, as a result of the above observation, the minimum line width with good rectangularity without pattern collapse was taken as an index for evaluation as "resolution". Furthermore, the minimum electron beam energy amount capable of drawing a good pattern shape was defined as "sensitivity" and used as an evaluation index.
Table 2 shows the evaluation results.

<Comparative Example 2>
A photoresist layer was directly formed on the SiO ₂ substrate in the same manner as in Example 2, except that no underlayer film was formed, to obtain a positive resist pattern. Table 2 shows the results.

As is clear from Table 1, Examples 1 and 2 using AlOH-XBisN-1 or AlOH-BisF-1 are superior to Comparative Example 1 in terms of heat resistance, solubility and etching resistance. was at least confirmed to be On the other hand, in Comparative Example 1 using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resin), the etching resistance was poor.
Moreover, in Examples 3 and 4, it was confirmed that the resist pattern shape after development was good and no defect was observed. Furthermore, it was confirmed that both resolution and sensitivity were significantly superior to Comparative Example 2 in which the formation of the underlayer film was omitted.
In addition, from the difference in the shape of the resist pattern after development, it was confirmed that the underlayer film-forming material for lithography used in Examples 3 and 4 had good adhesion to the resist material.

<Examples 5-6>
The solution of the underlayer film forming material for lithography of Examples 1 and 2 was applied onto a 300 nm-thickness SiO ₂ substrate and baked at 240° C. for 60 seconds and further at 400° C. for 120 seconds to obtain an underlayer with a thickness of 80 nm. A film was formed. A silicon-containing intermediate layer material is applied onto the underlayer film,
By baking at 200° C. for 60 seconds, an intermediate layer film with a film thickness of 35 nm was formed. Further, the ArF resist solution was applied onto the intermediate layer film and baked at 130° C. for 60 seconds to form a photoresist layer with a thickness of 150 nm. A silicon atom-containing polymer obtained below was used as the silicon-containing intermediate layer material.

16.6 g of 3-carboxylpropyltrimethoxysilane, 7.9 g of phenyltrimethoxysilane, and 14.4 g of 3-hydroxypropyltrimethoxysilane were dissolved in 200 g of tetrahydrofuran (THF) and 100 g of pure water, and the liquid temperature was raised to 35°C. and 5 g of oxalic acid
was added dropwise, and then the temperature was raised to 80° C. to carry out condensation reaction of silanol. Next, add 200 g of diethyl ether to separate the water layer, wash the organic liquid layer twice with ultrapure water, add 200 g of propylene glycol monomethyl ether acetate (PGMEA), and heat the liquid to 60°C under reduced pressure. After removing THF and diethyl ether water, a silicon atom-containing polymer was obtained.

Then, using an electron beam lithography system (manufactured by Elionix; ELS-7500, 50 keV), the photoresist layer is mask-exposed and baked (PEB) at 115° C. for 90 seconds.
A positive resist pattern of 55 nm L/S (1:1) was obtained by developing for 60 seconds with an 8 mass % tetramethylammonium hydroxide (TMAH) aqueous solution.

After that, using RIE-10NR manufactured by Samco International Co., Ltd., the silicon-containing intermediate layer film (SOG) is dry-etched using the obtained resist pattern as a mask,
Subsequently, the underlayer film was dry-etched using the obtained silicon-containing intermediate layer film pattern as a mask, and the SiO ₂ film was dry-etched using the obtained underlayer film pattern as a mask.

Each etching condition is as shown below.
Conditions for etching the resist pattern to the resist intermediate layer film
Output: 50W
Pressure: 20Pa
Time: 1 minute
Etching gas Ar gas flow rate: CF4 gas flow rate: _O2 gas flow rate = 50: ₈ :2 (sccm)
Conditions for etching the resist intermediate film pattern to the resist underlayer film
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF4 gas flow rate: _O2 gas flow rate = 50: ₅ :5 (sccm)
Etching conditions for the SiO ₂ film of the resist underlayer film pattern
Output: 50W
Pressure: 20Pa
Time: 2min
_Etching gas Ar gas flow rate: _C5F12 gas flow rate: _C2F6 gas flow rate: _{O2 gas} flow rate
= 50:4:3:1 (sccm)

[evaluation]
When the cross section of the pattern obtained as described above (the shape of the SiO ₂ film after etching) was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., it was found that the underlayer film of this embodiment was used. It was confirmed that, in the example, the shape of the SiO ₂ film after etching in the multi-layer resist processing was rectangular, and no defects were observed.

As described above, the present invention is not limited to the above embodiments and examples, and can be modified as appropriate without departing from the scope of the invention.

The compound and resin according to the present invention have high solubility in a safe solvent, good heat resistance and etching resistance, and the resist composition according to the present invention gives a good resist pattern shape.

In addition, it is possible to realize a compound, a resin, and a film-forming composition for lithography that are applicable to a wet process and are useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance. Further, since this film-forming composition for lithography uses a compound or resin having a specific structure, which has high heat resistance and high solvent solubility, deterioration of the film during high-temperature baking is suppressed, and oxygen plasma etching or the like is performed. It is possible to form a resist and an underlayer film that are also excellent in etching resistance to. Furthermore, when an underlayer film is formed, the adhesiveness to the resist layer is also excellent, so an excellent resist pattern can be formed.

Furthermore, it is useful as a composition for forming various optical parts because it has a high refractive index and can be prevented from being colored by low-temperature to high-temperature treatment.

Therefore, the present invention provides, for example, electrical insulating materials, resist resins, semiconductor sealing resins, printed wiring board adhesives, electrical laminates mounted in electrical equipment, electronic equipment, industrial equipment, etc., electrical equipment・Matrix resins for prepregs mounted on electronic and industrial equipment, build-up laminate materials, resins for fiber-reinforced plastics, sealing resins for liquid crystal display panels, paints,
Various coating agents, adhesives, coating agents for semiconductors, resist resins for semiconductors,
In addition to being used in resins for forming lower layer films, films, and sheets, plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses,
contrast enhancement lens, etc.), retardation film, electromagnetic wave shielding film, prism,
It can be widely and effectively used in optical components such as optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, and photosensitive optical waveguides.

INDUSTRIAL APPLICABILITY The present invention has industrial applicability in the fields of resists for lithography, underlayer films for lithography, underlayer films for multilayer resists, and optical components.

Claims (18)

A compound represented by the following formula (0).

(0)
(In formula (0), ^RY is a hydrogen atom,
R ^Z is an N-valent group having 1 to 60 carbon atoms or a single bond,
Each R ^T is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
an alkenyl group of up to 30, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl The groups, said alkenyl groups and said alkoxy groups may contain ether linkages, ketone linkages or ester linkages, wherein at least one of ^RT is a hydroxyl group and at least one of ^RT is a carbon number 2 to 30 alkenyl groups,
X represents an oxygen atom, a sulfur atom, a single bond or no cross-linking,
m is each independently an integer from 0 to 9, wherein at least one of m is an integer from 2 to 9 or at least two of m are integers from 1 to 9;
N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas in N [ ] may be the same or different,
Each r is independently an integer of 0-2. ) 2. The compound according to claim 1, wherein the compound represented by the formula (0) is a compound represented by the following formula (1).

(1)
(In formula (1), R ⁰ has the same meaning as R ^Y above,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
each of R ² to R ⁵ is independently an optionally substituted alkyl group having 1 to 30 carbon atoms;
optionally substituted C6-30 aryl group, optionally substituted C2-30 alkenyl group, optionally substituted C1-30 an alkoxy group of
a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond. well, at least one of R ² to R ⁵ is at least one hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms,
m ² and m ³ are each independently an integer of 0 to 8;
m ⁴ and m ⁵ are each independently an integer of 0 to 9, provided that m ² , m ³ , m ⁴ and m ⁵ are not 0 at the same time, m ² , m ³ and m ⁴ and at least one of m ⁵ is 2 to 8 or 2 to
an integer of 9 or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers from 1 to 8 or from 1 to 9;
n is the same as the above N, where n is an integer of 2 or more, n structural formulas in [ ] may be the same or different,
p ² to p ⁵ are each independently the same as r above. ) 2. The compound according to claim 1, wherein the compound represented by the formula (0) is a compound represented by the following formula (2).

(2)
(In formula (2), R ^0A is synonymous with R ^Y above,
R ^1A is an n ^A -valent group having 1 to 30 carbon atoms or a single bond,
Each R ^2A is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
an alkenyl group of up to 30, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl The groups, said alkenyl groups and said alkoxy groups, may contain ether linkages, ketone linkages or ester linkages, wherein at least one of R ^2A is at least one hydroxyl group and at least one of R ^2A is is an alkenyl group having 2 to 30 carbon atoms,
n ^A has the same definition as the above N, where n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom, a single bond or no cross-linking,
each m ^2A is independently an integer from 0 to 7, with the proviso that at least one m ^2A is an integer from 2 to 7 or at least two m ^2A are an integer from 1 to 7;
q ^A is each independently 0 or 1; ) The compound according to claim 2, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

(1-1)
(in formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are as defined above;
each of R ⁶ to R ⁷ is independently an optionally substituted alkyl group having 1 to 30 carbon atoms;
optionally substituted aryl group having 6 to 30 carbon atoms, alkenyl group having optionally substituted carbon atoms of 2 to 30, halogen atom, nitro group, amino group, carboxylic acid group or thiol a group, wherein at least one of R ⁶ to R ⁷ is an alkenyl group having 2 to 30 carbon atoms;
R ¹⁰ to R ¹¹ are each independently a hydrogen atom,
m ⁶ and m ⁷ are each independently an integer of 0 to 7, provided that m ⁴ , m ⁵ , m ⁶ and m ⁷ are not 0 at the same time. ) The compound according to claim 4, wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).

(1-2)
(in formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are as defined above;
R ⁸ to R ⁹ have the same definitions as R ⁶ to R ⁷ above;
R ¹² to R ¹³ have the same definitions as R ¹⁰ to R ¹¹ ;
m ⁸ and m ⁹ are each independently an integer of 0 to 8, provided that m ⁶ , m ⁷ , m ⁸ and m ⁹ are not 0 at the same time. ) The compound according to claim 3, wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).

(2-1)
(in formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A are as defined above;
Each R ^3A is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
-30 alkenyl groups, halogen atoms, nitro groups, amino groups, carboxylic acid groups or thiol groups, wherein at least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms;
each R ^4A is independently a hydrogen atom,
Each m ^6A is independently an integer of 0-5. ) A resin obtained by using the compound according to claim 1 as a monomer. 8. The resin according to claim 7, having a structure represented by the following formula (3).

(3)
(In the formula (3), L is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may have a substituent, 6 to 6 carbon atoms which may have a substituent, 30 arylene group, optionally substituted alkoxylene group having 1 to 30 carbon atoms or a single bond, wherein the alkylene group, the arylene group and the alkoxylylene group are an ether bond, a ketone bond or an ester may contain a bond,
R ⁰ has the same definition as R ^Y above,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
each of R ² to R ⁵ is independently an optionally substituted alkyl group having 1 to 30 carbon atoms;
optionally substituted C6-30 aryl group, optionally substituted C2-30 alkenyl group, optionally substituted C1-30 an alkoxy group of
a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond. well, at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms,
m ² and m ³ are each independently an integer of 0 to 8;
m ⁴ and m ⁵ are each independently an integer of 0 to 9, provided that m ² , m ³ , m ⁴ and m ⁵ are not 0 at the same time, m ² , m ³ and m ⁴ and at least one of m ⁵ is 2 to 8 or 2 to
An integer of 9 or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers of 1-8 or 1-9. ) 8. The resin according to claim 7, having a structure represented by the following formula (4).

(4)
(In formula (4), L is a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond,
R ^0A has the same definition as R ^Y above,
R ^1A is an n ^A -valent group having 1 to 30 carbon atoms or a single bond,
Each R ^2A is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. carbon number 2
an alkenyl group of up to 30, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl The groups, the alkenyl groups and the alkoxy groups may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R ^2A is a hydroxyl group and at least one of R ^2A is a carbon number 2 to 30 alkenyl groups,
n ^A has the same definition as the above N, where n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom, a single bond or no cross-linking,
each m ^2A is independently an integer from 0 to 7, with the proviso that at least one m ^2A is an integer from 2 to 7 or at least two m ^2A are an integer from 1 to 7;
q ^A is each independently 0 or 1; ) A composition comprising one or more selected from the group consisting of the compound according to any one of claims 1 to 6 and the resin according to any one of claims 7 to 9. 11. The composition of Claim 10, further comprising a solvent. 12. The composition according to claim 10 or 11, further comprising an acid generator. A composition according to any one of claims 10 to 12, further comprising an acid cross-linking agent. The composition according to any one of claims 10 to 13, which is a film-forming composition for lithography. The composition according to any one of claims 10 to 13, which is an optical component-forming composition. 15. A method of forming a resist pattern, comprising forming a photoresist layer on a substrate using the composition according to claim 14, and then irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer. An underlayer film is formed on a substrate using the composition according to claim 14, and after forming at least one photoresist layer on the underlayer film, a predetermined region of the photoresist layer is irradiated with radiation. and developing a resist pattern. An underlayer film is formed on a substrate using the composition according to claim 14, an intermediate layer film is formed on the underlayer film using a resist intermediate layer film material, and at least one layer is formed on the intermediate layer film. forming a photoresist layer of
a step of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern;
The intermediate layer film is etched using the resist pattern as a mask, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask. A method of forming a circuit pattern, comprising: forming a pattern.