JP7452947B2 - Compounds, resins, compositions, resist pattern forming methods, and circuit pattern forming methods - Google Patents

Description

The present invention relates to compounds, resins, and compositions having specific structures, as well as methods for forming resist patterns and circuit patterns.

In the manufacture of semiconductor devices, microfabrication is performed by lithography using photoresist materials, but in recent years, as LSIs become more highly integrated and operate at higher speeds, further miniaturization using pattern rules is required. In addition, the wavelength of the lithography light source used for 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 of the resist material is large, ranging from 10,000 to 100,000, and the molecular weight distribution is wide, resulting in roughness on the pattern surface, making it difficult to control pattern dimensions, and limiting miniaturization. There is. Therefore, various low molecular weight resist materials have been proposed to provide resist patterns with higher resolution. Since low molecular weight resist materials have small molecular sizes, they are expected to provide resist patterns with high resolution and low roughness.

Currently, various types of low molecular weight resist materials are known. For example, an alkali-developable negative-tone radiation-sensitive composition (see, for example, Patent Document 1 and Patent Document 2) using a low molecular weight polynuclear polyphenol compound as a main component has been proposed, and a low molecular weight resist material with high heat resistance has been proposed. As a candidate, an alkali-developable negative-tone 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. Furthermore, as a base compound for resist materials, polyphenol compounds can impart high heat resistance despite having a low molecular weight, and are known to be useful for improving the resolution and roughness of resist patterns (for example, Non-Patent Document 2 reference).

The present inventors have developed a resist composition containing a compound with a specific structure and an organic solvent (for example, Patent Document 4 ) is proposed.

Further, as resist patterns become finer, problems such as resolution problems or resist patterns collapsing after development arise, so it is desired to make resists thinner. However, simply thinning the resist makes it difficult to obtain a resist pattern with a thickness sufficient for substrate processing. Therefore, a process is required in which not only a resist pattern but also a resist underlayer film is created between the resist and the semiconductor substrate to be processed, and this resist underlayer film also functions as a mask during substrate processing.

Currently, various types of resist underlayer films for such processes are known. For example, unlike conventional resist underlayer films that have a fast etching rate, a resist underlayer film for lithography with a dry etching rate selectivity close to that of the resist can be realized by applying a predetermined energy to remove terminal groups. A lower layer film forming material for a multilayer resist process has been proposed, which contains a resin component having at least a substituent that separates to form a sulfonic acid residue, and a solvent (see, for example, Patent Document 5). In addition, resist underlayer film materials containing polymers having specific repeating units have been proposed to realize resist underlayer films for lithography that have a dry etching rate selectivity smaller than that of resists (for example, Patent Document (see 6). Furthermore, in order to realize a resist underlayer film for lithography that has a dry etching rate selectivity lower than that of semiconductor substrates, we have copolymerized repeating units of acenaphthylenes with repeating units having substituted or unsubstituted hydroxy groups. A resist underlayer film material containing a polymer has been proposed (for example, see Patent Document 7).

On the other hand, as a material having high etching resistance in this type of resist underlayer film, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas, etc. as a raw material is well known. However, from a process standpoint, there is a need 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 developed a composition for forming an underlayer film for lithography that contains a compound with a specific structure and an organic solvent as a material that has excellent etching resistance, high heat resistance, is soluble in solvents, and is applicable to wet processes. (For example, see Patent Document 8).

Furthermore, regarding the method for forming the intermediate layer used in forming the resist underlayer film in the three-layer process, for example, a method for forming a silicon nitride film (see, for example, Patent Document 9), a method for forming a silicon nitride film by CVD (for example, (see Patent Document 10) is known. Further, as an intermediate layer material for a three-layer process, a material containing a silsesquioxane-based silicon compound is known (see, for example, Patent Documents 11 and 12).

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

Japanese Patent Application Publication No. 2005-326838 Japanese Patent Application Publication No. 2008-145539 JP2009-173623A International Publication No. 2013/024778 Japanese Patent Application Publication No. 2004-177668 Japanese Patent Application Publication No. 2004-271838 JP2005-250434A International Publication No. 2013/024779 Japanese Patent Application Publication No. 2002-334869 International Publication No. 2004/066377 Japanese Patent Application Publication No. 2007-226170 Japanese Patent Application Publication No. 2007-226204 Japanese Patent Application Publication No. 2010-138393 Japanese Patent Application Publication No. 2015-174877 International Publication No. 2014/123005

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

As mentioned above, many lithography film-forming compositions for resist applications and lithography film-forming compositions for underlayer film applications have been proposed, but wet processes such as spin coating and screen printing can be applied. There is no material that not only has high solvent solubility but also has high heat resistance and etching resistance, and there is a need for the development of a new material.

In addition, although many compositions for optical members have been proposed in the past, none have achieved high levels of heat resistance, transparency, and refractive index, and there is a need for the development of new materials.

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

（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、Ｒ^０は、前記Ｒ^Ｙと同義であり、
Ｒ^１は、炭素数１～６０のｎ価の基又は単結合であり、
Ｒ^２～Ｒ^５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^２～Ｒ^５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^２～Ｒ^５の少なくとも１つは炭素数２～３０のアルケニル基であり、
ｍ^２及びｍ^３は、各々独立して、０～８の整数であり、
ｍ^４及びｍ^５は、各々独立して、０～９の整数であり、但し、ｍ^２、ｍ^３、ｍ^４及びｍ^５は同時に０になることはなく、ｍ^２、ｍ^３、ｍ^４及びｍ^５の少なくとも１つは２～８若しくは２～９の整数又はｍ^２、ｍ^３、ｍ^４及びｍ^５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、
ｐ^２～ｐ^５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、Ｒ^０、Ｒ^１、Ｒ^４、Ｒ^５、ｎ、ｐ^２～ｐ^５、ｍ^４及びｍ^５は、前記と同義であり、
Ｒ^６～Ｒ^７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^６～Ｒ^７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^１０～Ｒ^１１は、各々独立して、水素原子であり、
ｍ^６及びｍ^７は、各々独立して、０～７の整数であり、但し、ｍ^４、ｍ^５、ｍ^６及びｍ^７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、Ｒ^０、Ｒ^１、Ｒ^６、Ｒ^７、Ｒ^１０、Ｒ^１１、ｎ、ｐ^２～ｐ^５、ｍ^６及びｍ^７は、前記と同義であり、
Ｒ^８～Ｒ^９は、前記Ｒ^６～Ｒ^７と同義であり、
Ｒ^１２～Ｒ^１３は、前記Ｒ^１０～Ｒ^１１と同義であり、
ｍ^８及びｍ^９は、各々独立して、０～８の整数であり、但し、ｍ^６、ｍ^７、ｍ^８及びｍ^９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、
Ｒ^０は、前記Ｒ^Ｙと同義であり、
Ｒ^１は、炭素数１～６０のｎ価の基又は単結合であり、
Ｒ^２～Ｒ^５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^２～Ｒ^５の少なくとも１つは水酸基であり、またＲ^２～Ｒ^５の少なくとも１つは炭素数２～３０のアルケニル基であり、
ｍ^２及びｍ^３は、各々独立して、０～８の整数であり、
ｍ^４及びｍ^５は、各々独立して、０～９の整数であり、但し、ｍ^２、ｍ^３、ｍ^４及びｍ^５は同時に０になることはなく、ｍ^２、ｍ^３、ｍ^４及びｍ^５の少なくとも１つは２～８若しくは２～９の整数又はｍ^２、ｍ^３、ｍ^４及びｍ^５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］
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］
前記架橋剤が、フェノール化合物、エポキシ化合物、シアネート化合物、アミノ化合物、ベンゾオキサジン化合物、メラミン化合物、グアナミン化合物、グリコールウリル化合物、ウレア化合物、イソシアネート化合物及びアジド化合物からなる群より選ばれる少なくとも１種である、［１３］に記載の組成物。
［１５］
前記架橋剤が、少なくとも１つのアリル基を有する、［１３］又は［１４］に記載の組成物。
［１６］
前記架橋剤の含有量が、固形成分の全質量の０．１～５０質量％である、［１３］～［１５］のいずれかに記載の組成物。
［１７］
架橋促進剤をさらに含有する、［１３］～１６］のいずれかに記載の組成物。
［１８］
前記架橋促進剤が、アミン類、イミダゾール類、有機ホスフィン類及びルイス酸からなる群より選ばれる少なくとも１種である、［１７］に記載の組成物。
［１９］
前記架橋促進剤の含有量が、固形成分の全質量の０．１～５質量％である、［１７］又は［１８］に記載の組成物。
［２０］
ラジカル重合開始剤をさらに含有する、［１０］～［１９］のいずれかに記載の組成物。
［２１］
前記ラジカル重合開始剤が、ケトン系光重合開始剤、有機過酸化物系重合開始剤及びアゾ系重合開始剤からなる群より選ばれる少なくとも１種である、［１０］～［２０］のいずれかに記載の組成物。
［２２］
前記ラジカル重合開始剤の含有量が、固形成分の全質量の０．０５～２５質量％である、［１０］～［２１］のいずれかに記載の組成物。
［２３］
リソグラフィー用膜形成に用いられる、［１０］～［２２］のいずれかに記載の組成物。
［２４］
レジスト永久膜形成に用いられる、［１０］～［２２］のいずれかに記載の組成物。
［２５］
光学部品形成に用いられる、［１０］～［２２］のいずれかに記載の組成物。
［２６］
基板上に、［２３］に記載の組成物を用いて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。
［２７］
基板上に、［２３］に記載の組成物を用いて下層膜を形成し、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。
［２８］
基板上に、［２３］に記載の組成物を用いて下層膜を形成し、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、現像してレジストパターンを形成し、その後、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。 As a result of intensive studies to solve the problems of the prior art described above, the present inventors discovered that the problems of the prior art described above could be solved by using a compound or resin having a specific structure, and thus completed the present invention. Ta.
That is, the present invention is as follows.
[1]
A compound represented by the following formula (0).

(0)
(In formula (0), R ^Y is a hydrogen atom,
R ^Z is an N-valent group having 1 to 60 carbon atoms or a single bond,
R ^T each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an optionally substituted alkenyl group with 2 to 30 carbon atoms, an optionally substituted alkoxy group with 1 to 30 carbon atoms, 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 group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond, where at least one of R ^T is a hydroxyl group, and R ^T at least one of is an alkenyl group having 2 to 30 carbon atoms,
X represents an oxygen atom, a sulfur atom, a single bond or a non-crosslink,
m are each independently an integer of 0 to 9, where at least one of m is an integer of 2 to 9, or at least two of m are integers of 1 to 9,
N is an integer from 1 to 4, where N is an integer of 2 or more, the N structural formulas in [ ] may be the same or different,
Each r is independently an integer of 0 to 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 the above R ^Y ,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
R ² to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. 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, a carboxylic acid group, a thiol group, or 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, and at least one of R 2 to R 5 is a hydroxyl group, and at least one of R ² to R ⁵ is at least one 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 from 0 to 9, provided that m ² , m ³ , m ⁴ and m ⁵ are never 0 at the same time, and m ² , m ³ , m ⁴ and at least one of m ⁵ is an integer of 2 to 8 or 2 to 9, or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9,
n has the same meaning as N above, where n is an integer of 2 or more, the n structural formulas in [ ] may be the same or different,
p ² to p ⁵ each independently have the same meaning as r. )
[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 has the same meaning as the above R ^Y ,
R ^1A is an n ^A -valent group or single bond having 1 to 30 carbon atoms,
^R2A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an optionally substituted alkenyl group with 2 to 30 carbon atoms, an optionally substituted alkoxy group with 1 to 30 carbon atoms, 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 group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond, where 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,
^nA is synonymous with the above N, where ^nA is an integer of 2 or more, the structural formulas in [ ] of ^nA may be the same or different,
^XA represents an oxygen atom, a sulfur atom, a single bond or no crosslink,
each m ^2A is independently an integer from 0 to 7, provided that at least one m ^2A is an integer from 2 to 7, or at least two m ^2A is an integer from 1 to 7;
q ^A is each independently 0 or 1. )
[4]
The compound according to [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 have the same meanings as above,
R ⁶ to R ⁷ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. is an alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group, which may have 2 to 30 carbon atoms, and at least one of R ⁶ to R ⁷ has 2 to 30 carbon atoms. ~30 alkenyl groups,
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 never 0 at the same time. )
[5]
The compound according to [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 have the same meanings as above,
R ⁸ to R ⁹ have the same meanings as R ⁶ to R ⁷ above,
R ¹² to R ¹³ have the same meanings as R ¹⁰ to R ¹¹ above,
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 never 0 at the same time. )
[6]
The compound according to [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 have the same meanings as above,
R ^3A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol group, where at least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms; can be,
R ^4A is each independently a hydrogen atom,
m ^6A are each independently an integer of 0 to 5. )
[7]
A resin obtained by using the compound described in [1] as a monomer.
[8]
The resin according to [7], which has a structure represented by the following formula (3).

(3)
(In formula (3), L is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may have a substituent, or a linear, branched or cyclic alkylene group having 6 to 30 carbon atoms which may have a substituent. 30 arylene groups, an alkoxylene group having 1 to 30 carbon atoms which may have a substituent, or a single bond, and the alkylene group, the arylene group, and the alkoxylene group are an ether bond, a ketone bond, or an ester bond. may include a bond,
R ⁰ has the same meaning as the above R ^Y ,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
R ² to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. 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, a carboxylic acid group, a thiol group, or 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, and at least one of R ² to R ⁵ is a hydroxy 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 from 0 to 9, provided that m ² , m ³ , m ⁴ and m ⁵ are never 0 at the same time, and m ² , m ³ , m ⁴ and at least one of m ⁵ is an integer of 2 to 8 or 2 to 9, or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9. )
[9]
The resin according to [7], which has 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 is synonymous with the above R ^Y ,
R ^1A is an n ^A -valent group or single bond having 1 to 30 carbon atoms,
^R2A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an optionally substituted alkenyl group with 2 to 30 carbon atoms, an optionally substituted alkoxy group with 1 to 30 carbon atoms, 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 group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond, where at least one of R ^2A is a hydroxyl group, and R ^2A at least one of is an alkenyl group having 2 to 30 carbon atoms,
^nA is synonymous with the above N, where ^nA is an integer of 2 or more, the structural formulas in [ ] of ^nA may be the same or different,
X ^A indicates an oxygen atom, a sulfur atom, a single bond or no crosslinking,
each m ^2A is independently an integer from 0 to 7, provided that at least one m ^2A is an integer from 2 to 7 or at least two m ^2A is 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 containing an acid generator.
[13]
The composition according to any one of [10] to [12], further containing a crosslinking agent.
[14]
The crosslinking agent is at least one selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amino compound, a benzoxazine compound, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an isocyanate compound, and an azide compound. , the composition according to [13].
[15]
The composition according to [13] or [14], wherein the crosslinking agent has at least one allyl group.
[16]
The composition according to any one of [13] to [15], wherein the content of the crosslinking agent is 0.1 to 50% by mass of the total mass of the solid component.
[17]
The composition according to any one of [13] to 16], further containing a crosslinking accelerator.
[18]
The composition according to [17], wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.
[19]
The composition according to [17] or [18], wherein the content of the crosslinking accelerator is 0.1 to 5% by mass of the total mass of the solid component.
[20]
The composition according to any one of [10] to [19], further containing a radical polymerization initiator.
[21]
Any one of [10] to [20], wherein the radical polymerization initiator is at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator. The composition described in .
[22]
The composition according to any one of [10] to [21], wherein the content of the radical polymerization initiator is 0.05 to 25% by mass of the total mass of the solid components.
[23]
The composition according to any one of [10] to [22], which is used for forming a film for lithography.
[24]
The composition according to any one of [10] to [22], which is used for forming a permanent resist film.
[25]
The composition according to any one of [10] to [22], which is used for forming an optical component.
[26]
A method for forming a resist pattern, comprising forming a photoresist layer on a substrate using the composition described in [23], and then irradiating a predetermined region of the photoresist layer with radiation and developing it.
[27]
After forming a lower layer film on a substrate using the composition described in [23] and forming at least one photoresist layer on the lower layer film, radiation is applied to a predetermined region of the photoresist layer. A resist pattern forming method including the steps of irradiating and developing.
[28]
A lower layer film is formed on the substrate using the composition described in [23], an intermediate layer film is formed on the lower layer film using a resist intermediate layer film material, and at least After forming one photoresist layer, a predetermined region of the photoresist layer is irradiated with radiation and developed to form a resist pattern, and then the intermediate layer film is etched using the resist pattern as a mask, A circuit pattern forming method comprising the steps of etching the lower layer film using the obtained intermediate layer film pattern as an etching mask, and etching the substrate using the obtained lower layer film pattern as an etching mask to form a pattern on the substrate.

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

Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as "this embodiment") will be described. Note that the following embodiments are examples for explaining the present invention, and the present invention is not limited only to the embodiments.

The compound, resin, and composition containing the same in this embodiment are applicable to a wet process and are useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance. In addition, since the composition in this embodiment uses a compound or resin with a specific structure that has high heat resistance and solvent solubility, deterioration of the film during high temperature baking is suppressed, and etching resistance against oxygen plasma etching etc. It is also possible to form excellent resists and underlying films. In addition, when a lower layer film is formed, it has excellent adhesion with the resist layer, so that an excellent resist pattern can be formed.
Furthermore, since it has a high refractive index and is inhibited from coloring due to heat treatment over a wide range from low to high temperatures, it is 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), R ^Y is a hydrogen atom,
R ^Z is an N-valent group having 1 to 60 carbon atoms or a single bond,
R ^T each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an optionally substituted alkenyl group with 2 to 30 carbon atoms, an optionally substituted alkoxy group with 1 to 30 carbon atoms, 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 group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond, where at least one of R ^T is a hydroxyl group, and R ^T at least one of is an alkenyl group having 2 to 30 carbon atoms,
X represents an oxygen atom, a sulfur atom, a single bond or a non-crosslink,
m are each independently an integer of 0 to 9, where at least one of m is an integer of 2 to 9, or at least two of m are integers of 1 to 9,
N is an integer from 1 to 4, where N is an integer of 2 or more, the N structural formulas in [ ] may be the same or different,
Each r is independently an integer of 0 to 2. )

R ^Y is a hydrogen atom. As the alkyl group, a linear, branched or cyclic alkyl group can be used. 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 this R ^Z. N is an integer of 1 to 4, and when N is an integer of 2 or more, the N structural formulas in [ ] may be the same or different. Note that the above N-valent group refers to 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 an alkylene group having 2 to 30 carbon atoms when N=3. 60 alkanepropyl group, and when N=4, it represents an alkanetetrayl group having 3 to 60 carbon atoms. Examples of the N-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group mentioned above also includes a bridged alicyclic hydrocarbon group. Further, 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.

R ^T each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an optionally substituted alkenyl group with 2 to 30 carbon atoms, an optionally substituted alkoxy group with 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, and a hydroxyl group. , 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, where at least one of R ^T is a hydroxyl group, and R ^T At least one of them contains an alkenyl group having 2 to 30 carbon atoms. Note that 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 a non-crosslink. When X is an oxygen atom or a sulfur atom, it is preferable because it tends to exhibit high heat resistance, and an oxygen atom is more preferable. preferable. From the viewpoint of solubility, X is preferably non-crosslinked. Furthermore, each m is independently an integer of 0 to 9, 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 moiety represented by the naphthalene structure is a monocyclic structure when r=0, a bicyclic structure when r=1, and a tricyclic structure when r=2. becomes. Each r is independently an integer of 0 to 2. The numerical range of m mentioned above is determined according to the ring structure determined by r.

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

（１）

(1)

In the above formula (1), R ⁰ has the same meaning as the above R ^Y and is a hydrogen atom. When R ⁰ is a hydrogen atom, heat resistance tends to be relatively high and 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 .
R ² to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. 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, a carboxylic acid group, a thiol group, or 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, and at least one of R ² to R ⁵ is a hydroxy 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, and m ⁴ and m ⁵ are each independently an integer of 0 to 9. However, m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time. 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 at least two of m ² , m ³ , m ⁴ and m ⁵ is an integer of 1 to 8 or 1 to 9. is an integer.
n has the same meaning as N above and is an integer from 1 to 4. Here, when n is an integer of 2 or more, the n structural formulas in [ ] may be the same or different.
Each of p ² to p ⁵ independently has the same meaning as r above, and is an integer of 0 to 2.

Note that the alkyl group, alkenyl group, and alkoxy group may be linear, branched, or cyclic groups.

Note that the above n-valent group refers to 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 an alkylene group having 1 to 30 carbon atoms when n=3. An alkanepropyl group having 2 to 60 carbon atoms, and when n=4, an alkantetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group mentioned above also includes a bridged alicyclic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

Further, 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 alicyclic hydrocarbon group mentioned above also includes a bridged alicyclic hydrocarbon group.

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

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

Furthermore, because it has a relatively low molecular weight and low viscosity, it can evenly fill every corner of the step, even on substrates with steps (particularly minute spaces or hole patterns), ensuring a flat film. As a result, a composition for forming an underlayer film for lithography using this composition has good embedding and planarization properties. Furthermore, since it is a compound having a relatively high carbon concentration, it can also provide high etching resistance.

Furthermore, since it has a high aromatic density, it has a high refractive index, and coloration is suppressed even by heat treatment over a wide range from low to high temperatures, so it is useful as a composition for forming various optical parts. Among these, compounds having quaternary carbon are preferred from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloration, and improving heat resistance and solvent solubility. Optical components include film and sheet components, as well as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast improvement lenses, etc.), retardation films, electromagnetic shielding films, It is useful as prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulation films for multilayer printed wiring boards, and photosensitive optical waveguides.

（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 crosslinking 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 have the same meanings as above,
R ⁶ to R ⁷ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. is an alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group, which may have 2 to 30 carbon atoms, and at least one of R ⁶ to R ⁷ has 2 to 30 carbon atoms. ~30 alkenyl groups,
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 never 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 further ease of crosslinking 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 have the same meanings as above,
R ⁸ to R ⁹ have the same meanings as R ⁶ to R ⁷ above,
R ¹² to R ¹³ have the same meanings as R ¹⁰ to R ¹¹ above,
m ⁸ and m ⁹ are each independently an integer of 0 to 8. However, m ⁶ , m ⁷ , m ⁸ and m ⁹ do not become 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 (1a) from the viewpoint of supplyability of raw materials.

（１ａ）

(1a)

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

The compound represented by the above formula (1a) is more preferably a compound represented by the following formula (1b) from the viewpoint of solubility in an organic solvent.

（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 explained in the above formula (1-1).

The compound represented by the above formula (1a) is even more preferably a compound represented by the following formula (1b') from the viewpoint of reactivity.

（１ｂ’）

(1b')

In the above formula (1b'), R ⁰ , R ¹ , R ⁴ , R ⁵ , m ⁴ , m ⁵ , and n have the same meaning 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 explained in the above formula (1-1).

The compound represented by the above formula (1b) is even more preferably a compound represented by the following formula (1c) from the viewpoint of solubility in an organic solvent.

（１ｃ）

(1c)

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

From the viewpoint of reactivity, the compound represented by the above formula (1b') is more preferably a compound represented by the following formula (1c').

（１ｃ’）

(1c')

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

Specific examples of the compound represented by the above formula (0) are illustrated below, but the compound represented by the formula (0) is not limited to the specific examples listed here.

In the ^{above formula} , where at least one of m is an integer from 2 to 9, or at least two of m is an integer from 1 to 9. Here, at least one of R ^T' is a hydroxyl group, and at least one of R ^T' is an alkenyl group having 2 to 30 carbon atoms.

Specific examples of the compound represented by the above formula (0) are further illustrated below, but the compounds are not limited to those listed here.

In the above formula, X has the same meaning as explained in the above formula (0), and R ^{Y' and} R ^Z' have the same meanings as R ^Y and R ^Z explained in the above formula (0). Furthermore, each R ^4A is independently a hydrogen atom.

Specific examples of the compound represented by the above formula (1) are illustrated below, but the compounds are not limited to those listed here.

In the above compound, R ² , R ³ , R ⁴ , and R ⁵ have the same meanings as explained in the above formula (1). m ² and m ³ are integers from 0 to 8, and m ⁴ and m ⁵ are integers from 0 to 9.
However, at least one selected from R ² , R ³ , R ⁴ , and R ⁵ is a hydroxyl group, and at least one selected from R ² , R ³ , R ⁴ , and R ⁵ is an alkenyl group having 2 to 30 carbon atoms. It is the basis. m ² , m ³ , m ⁴ , and m ⁵ never become 0 at the same time.

The compound represented by the above formula (1) is particularly preferably a compound represented by the following formulas (BiF-1) to (BiF-5) from the viewpoint of further solubility in an organic solvent (specific examples (R ¹⁰ to R ¹³ therein have the same meanings as above).

（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, an alkyl group having 1 to 30 carbon atoms which may have a substituent, Aryl group having 6 to 30 carbon atoms which may have a substituent, alkenyl group having 2 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amino group, carboxylic acid group or thiol Here, at least one of R ^6' to R ^9' is an alkenyl group having 2 to 30 carbon atoms, and R ¹⁰ to R ¹³ have the same meaning as explained in the above formula (1c).

In the above formula, R ¹⁰ to R ¹³ have the same meaning as explained in the above formula (1-2), and R ¹⁴ each independently represents a linear, branched, or cyclic alkyl having 1 to 30 carbon atoms. group, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, or a thiol group, m ¹⁴ is an integer of 0 to 5, m ^14' is an integer from 0 to 4, and m ^14'' is an integer from 0 to 3.

^R14 is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group. group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triaconthoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, and thiol group. .

Each of the above examples of R ¹⁴ includes isomers. For example, the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meaning as explained in the above formula (1-2), and R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, These include an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.

^R15 is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group. group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triaconthoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, and thiol group. .

Each of the above examples of R ¹⁵ includes isomers. For example, the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.

Further, the compound represented by the above formula is preferably a compound represented by the following structure from the viewpoint of etching resistance.

In the above formula, R ^0A has the same meaning as the above formula R ^Y , R ^1A' has the same meaning as R ^Z , and R ¹⁰ to R ¹³ have the same meaning as explained in the above formula (1-2).

R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, or an alkenyl group having 1 to 30 carbon atoms. is an alkoxy group, a halogen atom, or a thiol group, and m ^14' is an integer of 0 to 4.

^R14 is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group. group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, and thiol group.

Each of the above examples of R ¹⁴ includes isomers. For example, the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meaning as explained in the above formula (1-2), and R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, These include an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.

^R15 is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group. group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, and thiol group.

Each of the above examples of R ¹⁵ includes isomers. For example, the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meaning as explained in the above formula (1-2), and R ¹⁶ is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, A divalent aryl group having 6 to 30 carbon atoms or a divalent alkenyl group having 2 to 30 carbon atoms.

^R16 is, for example, a methylene group, an ethylene group, a propene group, a butene group, a pentene group, a hexene group, a heptene group, an octene group, a nonene group, a decene group, an undecene group, a dodecene group, a triacontene group, a cyclopropene group, Cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriacontene group, divalent norbornyl group, divalent adamantyl group, divalent Examples include phenyl group, divalent naphthyl group, divalent anthracene group, divalent heptacene group, divalent vinyl group, divalent allyl group, and divalent triacontenyl group.

Each of the above examples of R ¹⁶ includes isomers. For example, the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meaning as explained in the above formula (1-2), and R ¹⁴ each independently represents a linear, branched, or cyclic alkyl having 1 to 30 carbon atoms. group, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, or a thiol group, and m ¹⁴ is an integer of 0 to 5.

^R14 is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group. group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, and thiol group.

Each of the above examples of R ¹⁴ includes isomers. For example, the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as explained in the above formula (1-2). The above formula preferably has a dibenzoxanthene skeleton from the viewpoint of heat resistance.

From the viewpoint of availability of raw materials, the above compounds are more preferably the compounds shown below.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as explained in the above formula (1-2). The above formula preferably has a dibenzoxanthene skeleton from the viewpoint of heat resistance.

The above formula is preferably represented by the following structure from the viewpoint of raw material availability, and more preferably a compound having a dibenzoxanthene skeleton from the viewpoint of heat resistance.

In the above formula, R ^0A has the same meaning as the above formula R ^Y , R ^1A' has the same meaning as R ^Z , and R ¹⁰ to R ¹³ have the same meaning as explained in the above formula (1-2). The above formula is more preferably a compound having a xanthene skeleton from the viewpoint of heat resistance.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as explained in the above formula (1-2), and R ¹⁴ , R ¹⁵ , R ¹⁶ , m ¹⁴ and m ^14' have the same meanings as above.

[Method for producing compound represented by formula (0)]
The compound represented by formula (0) in this embodiment can be appropriately synthesized by applying a known method, and the synthesis method is not particularly limited. Hereinafter, the compound represented by formula (0) will be explained using the compound represented by formula (1) as an example.
For example, a polyphenol compound is obtained by polycondensation reaction of biphenols, binaphthols, or bianthracenol and the corresponding aldehyde under an acid catalyst under normal pressure, and then at least one phenolic compound of the polyphenol compound is obtained. It can be obtained by introducing an allyl group into a hydroxyl group and then heating it to cause Claisen rearrangement. Moreover, it can also be carried out under pressure if necessary.

The timing of introducing the allyl group may be before or after the condensation reaction, or after the production of the resin described below.

Examples of the above-mentioned biphenols include, but are not limited to, biphenol, methylbiphenol, methoxybinaphthol, and the like. These can be used alone or in combination of two or more. 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 alone or in combination of two or more. Among these, it is more preferable to use binaphthol from the viewpoint of increasing the carbon atom concentration and improving heat resistance.

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, and biphenylaldehyde. Do, Examples include, but are not limited to, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural. These can be used alone or in combination of two or more. 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, and furfural, and from the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenyl It is more preferable to use aldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural.

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 is not particularly limited. Inorganic acids and organic acids are widely known as such acid catalysts, such as inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic 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 naphthalene disulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid, etc. However, it is not particularly limited to these. Among these, organic acids and solid acids are preferred from a manufacturing standpoint, and hydrochloric acid or sulfuric acid is more preferably used from a manufacturing viewpoint such as ease of availability and handling. In addition, regarding the acid catalyst, one type can be used alone or two or more types can be used in combination. Further, the amount of the acid catalyst to be used can be appropriately set depending on the type of raw materials and catalyst used, as well as the reaction conditions, etc., and is not particularly limited, but is 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw materials. It is preferable that

A reaction solvent may be used during the above reaction. The reaction solvent is not particularly limited as long as the reaction between the aldehyde used and the biphenols, binaphthols or bianthracenediol proceeds, and any known solvent can be appropriately selected and used. Examples of the reaction solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and a mixed solvent thereof. In addition, one type of solvent can be used alone or two or more types can be used in combination.

In addition, the amount of these reaction solvents to be used can be appropriately set depending on the types of raw materials and catalysts used, as well as reaction conditions, etc., and is not particularly limited, but may be 0 to 2000 parts by mass per 100 parts by mass of reaction materials. Preferably, the range is within the range. Further, the reaction temperature in the above reaction can be appropriately selected depending on the reactivity of the reaction raw materials, and is usually in the range of 10 to 200°C, although it is not particularly limited.

In order to obtain a polyphenol compound, the reaction temperature is preferably high, and specifically preferably in the range of 60 to 200°C. In addition, the reaction method can be appropriately selected and used, and is not particularly limited, but includes a method of charging biphenols, binaphthols or bianthracenediol, aldehydes, and a catalyst all at once, Alternatively, a method of dropping bianthracenediol or aldehydes in the presence of a catalyst may be mentioned. After the completion of the polycondensation reaction, the obtained compound can be isolated 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, common methods such as raising the temperature of the reaction vessel to 130 to 230°C and removing volatile components at about 1 to 50 mmHg are adopted. By doing so, the target compound can be isolated.

Preferred reaction conditions include using 1 mol to excess of biphenols, binaphthols, or bianthracenediol and 0.001 to 1 mol of an acid catalyst per 1 mol of aldehyde, at normal pressure, and at 50 to 150°C. For example, the reaction may be carried out for about 20 minutes to 100 hours.

After the reaction is completed, the target product can be isolated by a known method. For example, concentrate the reaction solution, add pure water to precipitate the reaction product, cool it to room temperature, filter it to separate it, filter the obtained solid, dry it, and then perform column chromatography. By separating and purifying the by-products, the solvent is distilled off, filtered, and dried to obtain the target compound represented by the above formula (1).

Furthermore, a method for 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.

The 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 thereto.

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

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

In this embodiment, the allyl group reacts in the presence of a radical or an acid/alkali, and its solubility in the acid, alkali, or organic solvent used in the coating solvent or developer changes. The allyl group-substituted group preferably has the property of causing a chain reaction in the presence of radicals or acids/alkali in order to enable pattern formation with even higher sensitivity and resolution.

[Resin obtained using the compound represented by 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 a film for lithography or forming an optical component. Further, a resin obtained by using the compound represented by the above formula (0) as a monomer can also be used as a composition. The resin is obtained, for example, by reacting the compound represented by the above formula (0) with a compound having crosslinking reactivity. Hereinafter, a resin obtained by using a compound represented by formula (0) as a monomer will be explained, taking as an example a resin obtained by using a compound represented by formula (1) as a monomer.

Examples of resins obtained 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 alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, or an arylene group having 6 to 30 carbon atoms which may have a substituent; The alkylene group, the arylene group, and the alkoxylene group may contain an ether bond, a ketone bond, or an ester bond. Moreover, the above-mentioned alkylene group and alkoxylene 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 have the same meanings as in the above formula (1).
However, m ² , m ³ , m ⁴ and m ⁵ are never 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 integer of 1 to 8 or 1 to 9; is an alkenyl group having 2 to 30 carbon atoms.

[Method for producing resin obtained using the 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 crosslinking reactivity. As the crosslinking-reactive compound, any known compound can be used without particular limitation as long as it can oligomerize or polymerize the compound represented by the above formula (1). Specific examples include aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, etc., but are not particularly limited thereto.

As a specific example of a resin having a structure represented by the above formula (3), for example, a condensation reaction of a compound represented by the above formula (1) with an aldehyde and/or a ketone that is a compound having crosslinking reactivity. Examples include novolak resins.

Here, examples of the aldehyde used when converting the compound represented by the above formula (1) into novolak 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, and furfural. Examples of ketones include the above-mentioned ketones. Among these, formaldehyde is more preferred. In addition, these aldehydes and/or ketones can be used individually or in combination of two or more types. Further, the amount of the aldehyde and/or ketone used is not particularly limited, but it is preferably 0.2 to 5 mol, more preferably 0.2 to 5 mol per mol of the compound represented by formula (1) above. The amount is 0.5 to 2 moles.

An acid catalyst can also be used in the condensation reaction between the compound represented by the above formula (1) and an aldehyde and/or ketone. The acid catalyst used here can be appropriately selected from known ones and is not particularly limited. Inorganic acids and organic acids are widely known as such acid catalysts; for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic 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 naphthalene disulfonic 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 preferred from the viewpoint of production such as ease of availability and handling. In addition, regarding the acid catalyst, one type can be used alone or two or more types can be used in combination.

In addition, the amount of the acid catalyst to be used can be appropriately set depending on the type of raw materials and catalyst used, as well as reaction conditions, etc., and is not particularly limited, but is 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw materials. It is preferable that However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene In the case of a copolymerization reaction with a compound having a non-conjugated double bond such as , limonene, aldehydes are not necessarily required.

A reaction solvent can also be used in the condensation reaction between the compound represented by formula (1) above and the aldehyde and/or ketone. The reaction solvent in this polycondensation can be appropriately selected from known ones and is not particularly limited, but examples include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof. Can be mentioned. In addition, one type of solvent can be used alone or two or more types can be used in combination.

In addition, the amount of these solvents to be used can be appropriately set depending on the types of raw materials and catalysts used, reaction conditions, etc., and is not particularly limited, but is in the range of 0 to 2000 parts by mass per 100 parts by mass of reaction raw materials. It is preferable that Further, the reaction temperature can be appropriately selected depending on the reactivity of the reaction raw materials, and is usually in the range of 10 to 200°C, although it is not particularly limited. Note that the reaction method can be appropriately selected and used from known methods, and is not particularly limited. Examples include a method in which a compound represented by the above formula (1), an aldehyde and/or a ketone is added dropwise in the presence of a catalyst.

After the completion of the polycondensation reaction, the obtained compound can be isolated 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, common methods such as raising the temperature of the reaction vessel to 130 to 230°C and removing volatile components at about 1 to 50 mmHg are adopted. By doing so, the desired product, the novolac-formed 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 it may not be a copolymer with other phenols. It's okay. Examples of phenols that can be copolymerized here include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Examples include, but are not limited to, propylphenol, pyrogallol, and thymol.

Further, the resin having the structure represented by the above formula (3) may be one copolymerized with a polymerizable monomer other than the other phenols mentioned 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, etc., but are not particularly limited thereto. Note that the resin having the structure represented by the above formula (3) is a copolymer of two or more elements (for example, a two to four element system) of the compound represented by the above formula (1) and the above-mentioned phenols. Even if the compound represented by the above formula (1) and the above-mentioned copolymerizable monomer are two or more (for example, 2- to 4-component system) copolymers, the compound represented by the above formula (1) The copolymer may be a ternary or more (for example, 3- to 4-component) copolymer of the above-mentioned compound, the above-mentioned phenols, and the above-mentioned copolymerizable monomer.

The molecular weight of the resin having the structure represented by the above formula (3) is not particularly limited, but it is preferable that the weight average molecular weight (Mw) in terms of polystyrene is 500 to 30,000, more preferably 750 to 20, It is 000. Furthermore, from the viewpoint of increasing crosslinking efficiency and suppressing volatile components during baking, the resin having the structure represented by the above formula (3) has a dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) of 1.2. It is preferably within the range of 7 to 7. Note that the above Mw and Mn can be determined by the method described in Examples described later.

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, when using 1-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 "resin mass ÷ (resin mass + solvent mass) x 100 (mass %)." For example, if 10 g of the resin dissolves in 90 g of PGMEA, the solubility of the resin in PGMEA will be "10% by mass or more," and if it does not dissolve, it will be "less than 10% by mass."

[Compound represented by formula (2)]
The compound represented by formula (0) in this embodiment is preferably a compound represented by formula (2) below from the viewpoint of heat resistance and solvent solubility.

（２）

(2)

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

Note that the above n-valent group refers to 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 an alkylene group having 1 to 30 carbon atoms when n=3. An alkanepropyl group having 2 to 60 carbon atoms, and when n=4, an alkantetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group mentioned above also includes a bridged alicyclic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

Further, 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 alicyclic hydrocarbon group mentioned above also includes a bridged alicyclic hydrocarbon group.

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

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

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

Furthermore, because it has a relatively low molecular weight and low viscosity, it can evenly fill every corner of the step, even on substrates with steps (particularly minute spaces or hole patterns), ensuring a flat film. As a result, a composition for forming an underlayer film for lithography using this composition has good embedding and planarization properties. Furthermore, since it is a compound having a relatively high carbon concentration, it can also provide high etching resistance.

Furthermore, since it has a high aromatic density, it has a high refractive index, and coloration is suppressed even by heat treatment over a wide range from low to high temperatures, so it is useful as a composition for forming various optical parts. Among these, compounds having quaternary carbon are preferred from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloration, and improving heat resistance and solvent solubility. Optical components include film and sheet components, as well as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast improvement lenses, etc.), retardation films, electromagnetic shielding films, It is useful as prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulation films for multilayer printed wiring boards, and photosensitive optical waveguides.

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 crosslinking and solubility in an organic solvent.

（２－１）

(2-1)

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

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

Further, the compound represented by the above formula (2-1) is more preferably a compound represented by the following formula (2a) from the viewpoint of supplyability of raw materials.

（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 an organic solvent.

（２ｂ）

(2b)

In the above formula (2b), X ^A , R ^0A , R ^1A , R ^3A , R ^4A , m ^6A and n ^A have the same meanings as those explained in the above formula (2-1).

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 an organic solvent.

（２ｃ）

(2c)

In the above formula (2c), X ^A , R ^0A , R ^1A , R ^3A , R ^4A , m ^6A and n ^A have the same meanings as those explained in the above formula (2-1).

The compounds represented by the above formula (2) are represented by the following formulas (BisN-1) to (BisN-4) and (XBisN-1) to (XBisN-3) from the viewpoint of further solubility in organic solvents. It is highly preferred that the compound is

（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)
In the above formulas (BisN-1) to (BisN-4) and (XBisN-1) to (XBisN-3), R ^3A and R ^4A have the same meanings as explained in the above formula (2-1). However, 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 this embodiment can be appropriately synthesized by applying a known method, and the synthesis method is not particularly limited.
For example, a polyphenol compound is obtained by polycondensation reaction of phenols, naphthols, and corresponding aldehydes or ketones under an acid catalyst under normal pressure, and then at least one phenolic hydroxyl group of the polyphenol compound is It can be obtained by introducing an allyl group into and then heating it to cause Claisen rearrangement. Moreover, it can also be carried out under pressure if necessary.

The timing of introducing the allyl group may be before or after the condensation reaction, or after the production of the resin described below.

The above-mentioned naphthols are not particularly limited and include, for example, naphthol, methylnaphthol, methoxynaphthol, naphthalene diol, etc. Among them, it is preferable to use naphthalene diol from the viewpoint that a xanthene structure can be easily created. .

The above-mentioned phenols are not particularly limited, and include, for example, 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, and biphenylaldehyde. Do, Examples include, but are not limited to, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural. These can be used alone or in combination of two or more. 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, and furfural, and from the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenyl It is more preferable to use aldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural.

The acid catalyst used in the above reaction can be appropriately selected from known ones and is not particularly limited. The acid catalyst can be appropriately selected from well-known inorganic acids and organic acids, such as inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, formic acid, and p-toluenesulfone. organic acids such as methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalene disulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride; Solid acids such as tungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid can be mentioned. Among these, it is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of production such as ease of availability and ease of handling. Regarding the acid catalyst, one type can be used alone or two or more types can be used in combination.

A reaction solvent may be used during the above reaction. The reaction solvent is not particularly limited as long as the reaction between the aldehyde used and the naphthol etc. proceeds, and for example, 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, and is, for example, in the range of 0 to 2000 parts by weight based on 100 parts by weight of the reaction raw materials.

The reaction temperature is not particularly limited and can be appropriately selected depending on 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 this embodiment with good selectivity, the temperature is preferably lower, and more preferably in the range of 10 to 60°C.

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

The amount of raw materials is not particularly limited, but for example, 2 moles to an excess of naphthols, etc. and 0.001 to 1 mole of an acid catalyst are used per 1 mole of aldehyde, at normal pressure, at 20 to 60°C. It is preferable to react for about 20 minutes to 100 hours.

After the reaction is completed, the target product is isolated by a known method. The method for isolating the target product is not particularly limited, and for example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, and after cooling to room temperature, the obtained solid is separated by filtration. An example of this method is to filter and dry the product, separate and purify it from by-products using column chromatography, and then perform solvent distillation, filtration, and drying to isolate the target compound.

Furthermore, a method for 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.

The 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 thereto.

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

In this embodiment, the allyl group reacts in the presence of a radical or an acid/alkali, and its solubility in the acid, alkali, or organic solvent used in the coating solvent or developer changes. The allyl group-substituted group preferably has the property of causing a chain reaction in the presence of radicals or acids/alkali in order to enable pattern formation with even higher sensitivity and resolution.

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

[Resin obtained using the compound represented by 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 components. Further, a resin obtained by using the compound represented by the above formula (2) as a monomer can be used as a composition. The resin is obtained, for example, by reacting the compound represented by the above formula (2) with a compound having crosslinking reactivity.

Examples of resins obtained 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 X ^A are synonymous with those in the above formula (2),
However, when n ^A is an integer of 2 or more, the n ^A structural formulas in [ ] may be the same or different, and at least one m ^2A is an integer from 2 to 6 or at least two m ^2A is an integer from 1 to 6, at least one of R ^2A is a hydroxyl group, and at least one is an alkenyl group having 2 to 30 carbon atoms.

[Method for producing resin obtained using the 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 crosslinking reactivity. As the crosslinking-reactive compound, any known compound can be used without particular limitation as long as it can oligomerize or polymerize the compound represented by the above formula (2). Specific examples include aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, etc., but are not particularly limited thereto.

As a specific example of the resin having the structure represented by the above formula (4), for example, the compound represented by the above formula (2) is subjected to a condensation reaction with an aldehyde and/or a ketone that is a compound having crosslinking reactivity. Examples include novolak resins.

Here, examples of the aldehyde used in novolakizing 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, and furfural. Examples of ketones include the above-mentioned ketones. Among these, formaldehyde is more preferred. In addition, these aldehydes and/or ketones can be used individually or in combination of two or more types. Further, the amount of the aldehyde and/or ketone used is not particularly limited, but it is preferably 0.2 to 5 mol, more preferably 0.2 to 5 mol per mol of the compound represented by formula (2) above. The amount is 0.5 to 2 moles.

An acid catalyst can also be used in the condensation reaction between the compound represented by the above formula (2) and the aldehyde and/or ketone. The acid catalyst used here can be appropriately selected from known ones and is not particularly limited. Inorganic acids and organic acids are widely known as such acid catalysts; for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic 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 naphthalene disulfonic 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 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 ease of availability and handling. In addition, regarding the acid catalyst, one type can be used alone or two or more types can be used in combination.

In addition, the amount of the acid catalyst to be used can be appropriately set depending on the type of raw materials and catalyst used, as well as reaction conditions, etc., and is not particularly limited, but is 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw materials. It is preferable that However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene In the case of a copolymerization reaction with a compound having a non-conjugated double bond such as , limonene, aldehydes are not necessarily required.

A reaction solvent can also be used in the condensation reaction between the compound represented by formula (2) above and the aldehyde and/or ketone. The reaction solvent in this polycondensation can be appropriately selected from known ones and is not particularly limited, but examples include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof. Can be mentioned. In addition, one type of solvent can be used alone or two or more types can be used in combination.

In addition, the amount of these solvents to be used can be appropriately set depending on the types of raw materials and catalysts used, reaction conditions, etc., and is not particularly limited, but is in the range of 0 to 2000 parts by mass per 100 parts by mass of reaction raw materials. It is preferable that Further, the reaction temperature can be appropriately selected depending on the reactivity of the reaction raw materials, and is usually in the range of 10 to 200°C, although it is not particularly limited. In addition, the reaction method can be appropriately selected and used, and is not particularly limited, but includes a method of charging the compound represented by the above formula (2), aldehyde and/or ketones, and a catalyst all at once, A method of dropping a compound represented by the above formula (2), an aldehyde and/or a ketone in the presence of a catalyst can be mentioned.

After the completion of the polycondensation reaction, the obtained compound can be isolated 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, common methods such as raising the temperature of the reaction vessel to 130 to 230°C and removing volatile components at about 1 to 50 mmHg are adopted. By doing so, the desired product, the novolac-formed 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 it may not be a copolymer with other phenols. You can. Examples of phenols that can be copolymerized here include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Examples include, but are not limited to, propylphenol, pyrogallol, and thymol.

Further, the resin having the structure represented by the above formula (4) may be copolymerized with a polymerizable monomer other than the other phenols mentioned 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, etc., but are not particularly limited thereto. The resin having the structure represented by the above formula (4) is a copolymer of two or more elements (for example, a two to four element system) of the compound represented by the above formula (2) and the above-mentioned phenols. Even if the compound represented by the above formula (2) and the above-mentioned copolymerizable monomer are two or more (for example, 2- to 4-component system) copolymers, the compound represented by the above formula (2) The copolymer may be a ternary or more (for example, 3- to 4-component) copolymer of the above-mentioned compound, the above-mentioned phenols, and the above-mentioned copolymerizable monomer.

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

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, when using 1-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) x 100 (mass%)". For example, if 10 g of the resin dissolves in 90 g of PGMEA, the solubility of the resin in PGMEA will be "10% by mass or more," and if it does not dissolve, it will be "less than 10% by mass."

[Compound and/or resin purification method]
More specifically, the method for purifying a compound and/or resin in this embodiment includes at least one of the compound represented by the above formula (0) or a resin obtained by using the compound represented by the above formula (0) as a monomer. 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 obtaining a solution (S) by dissolving one or more resins obtained using a compound as a monomer in a solvent, and bringing the obtained solution (S) into contact with an acidic aqueous solution to dissolve the compound and/or Alternatively, the method includes a step of extracting impurities in the resin (first extraction step), and the solvent used in the step of obtaining the solution (S) includes a solvent that is arbitrarily immiscible with water.
In the first extraction step, the resin may be a resin obtained by reacting the compound represented by the above formula (1) and/or the compound represented by the formula (2) with a compound having crosslinking reactivity. preferable. According to the purification method of this embodiment, the content of various metals that may be contained as impurities in the compound or resin having the above-described specific structure can be reduced.
More specifically, in the purification method of the present embodiment, the compound and/or the resin are dissolved in an organic solvent that is not miscible with water to obtain a solution (S), and the solution (S) is further dissolved in an organic solvent that is not miscible with water. Extraction treatment can be performed by contacting with an acidic aqueous solution. Thereby, after the metal content contained in the solution (S) is transferred to the aqueous phase, the organic phase and the aqueous phase can be separated to obtain a compound and/or resin with a reduced metal content.

The compounds and/or resins used in the purification method of this embodiment may be used alone or in combination of two or more. Further, the above compounds and resins may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers, and the like.

The solvent that is arbitrarily immiscible with water used in the purification method of the present embodiment is not particularly limited, but organic solvents that can be safely applied to semiconductor manufacturing processes are preferable, and 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 total amount of the compound and resin used.

Specific examples of solvents that are not miscible with water 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 ketones, 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 Examples include 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 preferred, methyl isobutyl ketone, ethyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate are more preferred, and methyl Isobutyl ketone and ethyl acetate are even more preferred. Methyl isobutyl ketone, ethyl acetate, etc. have relatively high saturation solubility and relatively low boiling points of the above compounds and resins containing the compounds as constituent components, so they are removed industrially when the solvent is distilled off or by drying. It becomes possible to reduce the load in the process. These solvents can be used alone or in combination of two or more.

The acidic aqueous solution used in the purification method of this 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 in which mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are dissolved in water; acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, and fumaric acid. Examples include aqueous organic acid solutions in which organic acids such as , maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid are 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, It is preferably an aqueous solution of one or more organic acids selected from the group consisting of tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid, including sulfuric acid, nitric acid, acetic acid, oxalic acid, Aqueous solutions of carboxylic acids such as tartaric acid and citric acid are more preferred, aqueous solutions of sulfuric acid, oxalic acid, tartaric acid and citric acid are even more preferred, and aqueous solutions of oxalic acid are even more preferred. It is thought that polyhydric carboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate with metal ions and produce a chelating effect, so that they tend to be able to remove metals more effectively. Further, as the water used here, it is preferable to use water with a low metal content, such as ion-exchanged water, in accordance 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 this embodiment is not particularly limited, it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the above-mentioned compounds and resins. The pH of the acidic aqueous solution is usually about 0 to 5, preferably about 0 to 3.

The amount of acidic aqueous solution used in the purification method of this embodiment is not particularly limited, but from the viewpoint of reducing the number of extractions for metal removal and ensuring operability by considering the total liquid volume, 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, based on 100% by mass of the solution (S).

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

In the purification method of this embodiment, it is preferable that the solution (S) further contains an organic solvent that is optionally miscible with water. When the solution (S) contains an organic solvent that is optionally miscible with water, the amount of the above-mentioned compound and/or resin can be increased, and the liquid separation properties are improved, allowing purification to be performed with high pot efficiency. tends to be possible. The method of adding an organic solvent that is optionally miscible with water is not particularly limited, and examples include adding it to a solution containing an organic solvent in advance, adding it to water or an acidic aqueous solution in advance, and adding the organic solvent to a solution containing an organic solvent and water or an acidic aqueous solution. Any method of adding after contact may be used. Among these, a method in which the organic solvent is added in advance to a solution containing an organic solvent is preferable from the viewpoint of operational efficiency and ease of controlling the amount to be charged.

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

Specific examples of organic solvents that are 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; Can be 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. These solvents can be used alone or in combination of two or more.

The temperature during the extraction process is usually 20 to 90°C, preferably 30 to 80°C. The extraction operation is carried out, for example, by thoroughly mixing the mixture by stirring or the like, and then allowing it to stand still. As a result, the metal contained in the solution (S) is transferred to the aqueous phase. Moreover, this operation lowers the acidity of the solution, making it possible to suppress deterioration of the compound and/or resin.

When the mixed solution is allowed to stand still, it is separated into a solution phase containing the compound and/or resin and the solvent and an aqueous phase, so the solution phase is recovered by decantation or the like. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of better separating the solution phase containing the solvent and the aqueous phase. Usually, the time for leaving still is 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more. Furthermore, although the extraction process may be performed only once, 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). It is preferable to include a step). Specifically, for example, after performing the above extraction treatment using an acidic aqueous solution, a solution phase containing the recovered compound and/or resin and solvent extracted from the aqueous solution is further subjected to an extraction treatment with water. It is preferable. This extraction treatment with water is not particularly limited, but can be carried out, for example, by thoroughly mixing the solution phase and water by stirring or the like, and then allowing the resulting mixed solution to stand still. The mixed solution after standing is separated into a solution phase containing the compound and/or resin and the solvent and an aqueous phase, so 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 accordance with the purpose of this embodiment. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating multiple times. Furthermore, the conditions such as the proportion of the two used, temperature, time, etc. in the extraction treatment are not particularly limited, but may be the same as in the case of the contact treatment with the acidic aqueous solution described above.

Moisture that may be mixed into the solution containing the compound and/or resin and solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. Further, if necessary, a solvent can be added to the above solution to adjust the concentration of the compound and/or resin to an arbitrary concentration.

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

[Composition]
The composition in this embodiment is a resin obtained by using a compound represented by the above formula (0) and a compound represented by the above formula (0) as monomers, more specifically a resin represented by the above formula (1). 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, a solvent, It contains one or more selected from the group consisting of acid generators, crosslinking agents, crosslinking accelerators, radical polymerization initiators, and the like.

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

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

Moreover, it is preferable that the composition (resist composition) in this embodiment further contains a solvent. Examples of the solvent include, but are not limited to, ethylene glycol monoalkyl ether acetate 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, n lactic acid - Lactic acid esters such as butyl and n-amyl lactate; aliphatic acids such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, and ethyl propionate. Carboxylic acid esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, Other esters such as 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate; toluene , aromatic hydrocarbons such as xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); N,N-dimethylformamide, N-methylacetamide, Examples include amides such as N,N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-lactone, but are not particularly limited to these. 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 at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate. It is a species, and more preferably at least one selected from PGMEA, PGME, and CHN.

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

The composition (resist composition) of the present embodiment has other solid components selected from the group consisting of an acid generator (C), a crosslinking agent (G), an acid diffusion control agent (E), and other components (F). It may further contain at least one selected one. Note that in this specification, the term "solid component" refers to components other than the solvent.

Here, for the acid generator (C), crosslinking agent (G), acid diffusion control agent (E) and other components (F), known ones can be used and are not particularly limited, but for example, International Publication No. 2013 The one described in No./024778 is preferred.

[Blending 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 the solid components (resist base material, acid generator (C), crosslinking agent (G ), the total amount of solid components including optionally used components such as acid diffusion control agent (E) and other components (F) (the same shall apply hereinafter)) is preferably 50 to 99.4% by mass, and more preferably The content is preferably 55 to 90% by weight, more preferably 60 to 80% by weight, particularly preferably 60 to 70% by weight. 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.
Note that when the resist base material contains both a compound and a resin, the above content is the total amount of both components.

[Other ingredients (F)]
The resist composition in this embodiment may optionally include a resist base material, an acid generator (C), a crosslinking agent (G), and an acid diffusion control agent (E) to the extent that the object of the present invention is not impaired. Components include dissolution promoters, dissolution control agents, sensitizers, surfactants, organic carboxylic acids or phosphorus oxoacids or derivatives thereof, thermal and/or photocuring catalysts, polymerization inhibitors, flame retardants, fillers, Coupling agents, thermosetting resins, photocuring resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants, etc. One or more types of additives can be added. Note that in this specification, other components (F) may be referred to as optional components (F).

In the resist composition of the present embodiment, a resist base material (hereinafter also referred to as "component (A)"), an acid generator (C), a crosslinking agent (G), an acid diffusion control agent (E), an optional component ( The content of F) (component (A) / acid generator (C) / crosslinking agent (G) / acid diffusion control agent (E) / optional component (F)) is mass % based on solid matter,
Preferably 50-99.4/0.001-49/0.5-49/0.001-49/0-49,
More preferably 55-90/1-40/0.5-40/0.01-10/0-5,
More preferably 60-80/3-30/1-30/0.01-5/0-1,
Particularly preferred range 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, performance such as sensitivity, resolution, developability, etc. tends to be excellent.

The resist composition of this embodiment is usually prepared by dissolving each component in a solvent to form a homogeneous solution at the time of use, and then, if necessary, filtering it with a filter having a pore size of about 0.2 μm, etc. Ru.

The resist composition of this embodiment can contain other resins other than the resin of this embodiment as long as the object of the present invention is not impaired. Other resins are not particularly limited, and include, for example, novolac resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and acrylic acid, vinyl alcohol, or vinylphenol as monomer units. and derivatives thereof. The content of other resins is not particularly limited and may be adjusted as appropriate depending on the type of component (A) used, but is preferably 30 parts by mass or less based on 100 parts by mass of component (A). , more preferably 10 parts by weight or less, further preferably 5 parts by weight or less, particularly preferably 0 parts by weight.

[Physical properties of resist composition, etc.]
Using the resist composition of this embodiment, an amorphous film can be formed by spin coating. Furthermore, the resist composition of this embodiment can be applied to general semiconductor manufacturing processes. 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, either a positive resist pattern or a negative resist pattern can be formed. It 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 this embodiment in a developer at 23°C is preferably 5 Å/sec or less, and 0.05 to 5 Å/sec. sec, more preferably 0.0005 to 5 Å/sec. When 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 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 compounds as constituent components before and after exposure, which causes the exposed areas to dissolve in the developer and the exposed areas to be dissolved in the developer. It is presumed that this is because the contrast at the interface with the unexposed area that is not dissolved increases. In addition, the effect of reducing LER and defects can be seen.

In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin coating the resist composition of this 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 suitable for resists. Further, when the dissolution rate is 10 Å/sec or more, resolution may be improved. This is presumed to be because the microscopic surface sites of the compound represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent are dissolved and the LER is reduced. The effect of reducing defects is also seen.

The dissolution rate can be determined by immersing the amorphous film in a developer for a predetermined time at 23° C., 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 portions of the amorphous film formed by spin coating the resist composition of this embodiment exposed to radiation such as KrF excimer laser, extreme ultraviolet rays, electron beams, or X-rays are resistant to developing solution 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 suitable for resists. Further, when the dissolution rate is 10 Å/sec or more, resolution may be improved. This is presumed to be because the microscopic surface sites of the compound represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent are dissolved and the LER is reduced. The effect of reducing defects is also seen.

In the case of a negative resist pattern, the parts of the amorphous film formed by spin coating the resist composition of this embodiment exposed to radiation such as KrF excimer laser, extreme ultraviolet rays, electron beams, or X-rays are treated with a developer at 23°C. The dissolution rate is preferably 5 Å/sec or less, more preferably 0.05 to 5 Å/sec, and even more preferably 0.0005 to 5 Å/sec. When 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 be improved. This is due to changes in the solubility of the compounds represented by formulas (1) and (2) above and/or resins containing these compounds as constituent components before and after exposure, resulting in an unexposed area that dissolves in the developer and a developer that dissolves in the developer. It is presumed that this is because the contrast at the interface with the exposed area that is not dissolved in the oxide increases. In addition, the effect of reducing LER and defects can be seen.

[Lithography film-forming composition for non-chemically amplified resist applications]
The component (A) to be contained in the lithography film-forming composition for non-chemically amplified resist applications (hereinafter also referred to as "radiation-sensitive composition") of the present embodiment is a diazonaphthoquinone photoactive compound (B) described below. A base material for positive resist that becomes a compound easily soluble in a developer by irradiating it with G-line, H-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet rays, electron beam or X-ray. It is useful as The properties of component (A) do not change significantly when exposed to g-rays, h-rays, i-rays, KrF excimer lasers, ArF excimer lasers, extreme ultraviolet rays, electron beams, or X-rays, but diazonaphthoquinone, which is sparingly soluble in developer, is photoactive. Since the compound (B) changes into an easily soluble compound, it becomes possible to create a resist pattern through the development process.

Since the component (A) contained in the radiation-sensitive composition of this embodiment is a compound with a relatively low molecular weight, the roughness of the resulting resist pattern is very small. Further, in the above formula (1), at least one selected from the group consisting of R ⁰ to R ⁵ is preferably a group containing an iodine atom, and in the above formula (2), R ^0A , R ^1A and It is preferable that at least one selected from the group consisting of R ^2A is a group containing an iodine atom. When the radiation-sensitive composition of the present embodiment is applied with the component (A) having a group containing an iodine atom, the absorption capacity for radiation such as electron beams, extreme ultraviolet (EUV), and X-rays increases, and as a result, , is preferable because it makes it possible to increase sensitivity.

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, even more preferably 140°C or higher, 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 component (A) is within the above range, it has heat resistance capable of maintaining pattern shape in a semiconductor lithography process, and tends to improve performance such as high resolution.

The crystallization heat value determined by differential scanning calorimetry analysis of the glass transition temperature of component (A) contained in the radiation-sensitive composition of the present embodiment is preferably less than 20 J/g. Further, (crystallization temperature) - (glass transition temperature) is preferably 70°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, particularly preferably 130°C or higher. When the crystallization calorific value is less than 20 J/g or (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 resist The film forming properties required for this tend to be maintained over a long period of time, and the resolution tends to be improved.

In the present embodiment, the crystallization calorific value, crystallization temperature, and glass transition temperature can be determined by differential scanning calorimetry using Shimadzu DSC/TA-50WS. Approximately 10 mg of the sample is placed in an unsealed aluminum container, and the temperature is raised to above the melting point in a nitrogen gas flow (50 mL/min) at a rate of 20° C./min. After quenching, the temperature is raised again to the melting point or higher in a nitrogen gas flow (30 mL/min) at a heating rate of 20°C/min. After further rapid cooling, the temperature is again raised to 400° C. in a nitrogen gas stream (30 mL/min) at a heating rate of 20° C./min. The temperature at the midpoint of the baseline step change (where the specific heat changes by half) is the glass transition temperature (Tg), and the temperature at the exothermic peak that appears thereafter is the crystallization temperature. The calorific value is determined from the area of the region surrounded by the exothermic peak and the baseline, and is taken as the crystallization calorific value.

The component (A) to be contained in the radiation-sensitive composition of the present embodiment is 100°C or less, preferably 120°C or less, more preferably 130°C or less, even more preferably 140°C or less, particularly preferably 150°C or less, under normal pressure. In this case, it is preferable that the sublimability is low. Low sublimation property means that, in 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, particularly preferably indicates that it is 0.1% or less. The low sublimation property makes it possible to prevent exposure equipment from being contaminated by outgas during exposure. Further, a good pattern shape can be obtained with low roughness.

Component (A) contained in the radiation-sensitive composition of the present embodiment is 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 exhibiting the highest solubility for component (A) at 23°C, preferably 1% by mass or more, more preferably is dissolved in an amount of 5% by mass or more, more preferably 10% by mass or more. Particularly preferably, at 23°C, 20% by mass or more, particularly preferably PGMEA, is added to a solvent selected from the group consisting of PGMEA, PGME, and CHN, and which exhibits the highest solubility for the (A) resist base material. On the other hand, at 23°C, 20% by mass or more dissolves. By satisfying the above conditions, it becomes easy to use the semiconductor manufacturing process in actual production.

[Diazonaphthoquinone photoactive compound (B)]
The diazonaphthoquinone photoactive compound (B) 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 photosensitive resist compositions. There are no particular limitations as long as they are used as photosensitive ingredients (photosensitizers), and one or more types can be arbitrarily selected and used.

Component (B) is a compound obtained by reacting naphthoquinonediazide sulfonic acid chloride, benzoquinonediazide sulfonic acid chloride, etc. with a low-molecular compound or a high-molecular compound having a functional group capable of condensation reaction with these acid chlorides. preferable. Here, the functional group capable of condensation with acid chloride is not particularly limited, and examples thereof include hydroxyl group, amino group, etc., and hydroxyl group is particularly preferred. Compounds that can be condensed with acid chloride containing a hydroxyl group are not particularly limited, and examples include hydroquinone, resorcinol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, and 2,4,6-trihydroxybenzophenone. , 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2',3,4,6' -Hydroxybenzophenones such as pentahydroxybenzophenone; hydroxyphenyl alkanes such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane Class: 4,4',3",4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',2",3",4"-pentahydroxy-3 , hydroxytriphenylmethanes such as 5,3',5'-tetramethyltriphenylmethane, and the like.
In addition, as acid chlorides such as naphthoquinonediazide sulfonic acid chloride and benzoquinonediazide sulfonic acid chloride, for example, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, etc. are preferred. Can be mentioned.

The radiation-sensitive composition of this embodiment is prepared, for example, by dissolving each component in a solvent to form a homogeneous solution at the time of use, and then, if necessary, filtering it with a filter having a pore size of about 0.2 μm, etc. It is preferable that

[Characteristics of radiation-sensitive composition]
Using the radiation-sensitive composition of this embodiment, an amorphous film can be formed by spin coating. Furthermore, the radiation-sensitive composition of this embodiment can be applied to general semiconductor manufacturing processes. Depending on the type of developer used, either a positive resist pattern or a negative resist pattern can be created.

In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment in a developer at 23°C is preferably 5 Å/sec or less, and 0.05 to More preferably, it is 5 Å/sec, and even more preferably 0.0005 to 5 Å/sec. When 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 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 compounds as constituent components before and after exposure, which causes the exposed areas to dissolve in the developer and the exposed areas to be dissolved in the developer. It is presumed that this is because the contrast at the interface with the unexposed area that is not dissolved increases. In addition, the effect of reducing LER and defects can be seen.

In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of this 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 suitable for resists. Further, when the dissolution rate is 10 Å/sec or more, resolution may be improved. This is presumed to be because the microscopic surface sites of the compound represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent are dissolved and the LER is reduced. The effect of reducing defects is also seen.

The above dissolution rate can be determined by immersing the amorphous film in a developer for a predetermined time at 23°C 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, after irradiating the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment with radiation such as KrF excimer laser, extreme ultraviolet rays, electron beams, or X-rays, or The dissolution rate of the exposed portion after heating at 500° C. in a developer at 23° C. is preferably 10 Å/sec or more, more preferably 10 to 10,000 Å/sec, and even more preferably 100 to 1,000 Å/sec. When the dissolution rate is 10 Å/sec or more, it is easily soluble in a developer and suitable for resists. Further, when the dissolution rate is 10,000 Å/sec or less, resolution may be improved. This is presumed to be because the microscopic surface sites of the compound represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent are dissolved and the LER is reduced. The effect of reducing defects is also seen.

In the case of a negative resist pattern, after irradiating the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment with radiation such as KrF excimer laser, extreme ultraviolet rays, electron beams, or X-rays, or The dissolution rate of the exposed portion after heating at 500°C in a developer at 23°C is preferably 5 Å/sec or less, more preferably 0.05 to 5 Å/sec, and 0.0005 to 5 Å/sec. More preferably, it is 5 Å/sec. When 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 be improved. This is due to changes in the solubility of the compounds represented by formulas (1) and (2) above and/or resins containing these compounds as constituent components before and after exposure, resulting in an unexposed area that dissolves in the developer and a developer that dissolves in the developer. It is presumed that this is because the contrast at the interface with the exposed area that is not dissolved in the oxide increases. In addition, the effect of reducing LER and defects can be seen.

[Blending ratio of each component]
In the radiation-sensitive composition of the present embodiment, the content of component (A) is determined according to the total mass of the solid components (component (A), diazonaphthoquinone photoactive compound (B), other components (D), etc.). It is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, even more preferably 10 to 90% by mass, particularly preferably 25 to 75% by mass, based on the total amount of solid components used (the same applies hereinafter). Mass%. When the content of 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 small roughness.

In the radiation-sensitive composition of the present embodiment, the content of the diazonaphthoquinone photoactive compound (B) is the total mass of the solid components (component (A), diazonaphthoquinone photoactive compound (B), and other components (D)). 1 to 99% by mass, more preferably 5 to 95% by mass, even more preferably 10 to 90% by mass, particularly preferably is 25 to 75% by mass. In the radiation-sensitive composition of the present embodiment, when the content of the diazonaphthoquinone photoactive compound (B) is within the above range, a pattern with high sensitivity and small roughness tends to be obtained.

[Other ingredients (D)]
The radiation-sensitive composition of the present embodiment may optionally contain an acid generator, a crosslinking agent, and other components other than the component (A) and the diazonaphthoquinone photoactive compound (B) within a range that does not impede the object of the present invention. agents, acid diffusion control agents, dissolution promoters, dissolution control agents, sensitizers, surfactants, organic carboxylic acids or phosphorus oxoacids or derivatives thereof, thermal and/or photocuring catalysts, polymerization inhibitors, flame retardants, Fillers, coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants One or more types of various additives such as the following can be added. In addition, in this specification, other components (D) may be referred to as optional components (D).

In the radiation-sensitive composition of this embodiment, the blending ratio of each component (component (A)/diazonaphthoquinone photoactive compound (B)/optional component (D)) is mass % based on solid components,
Preferably 1-99/99-1/0-98,
More preferably 5-95/95-5/0-49,
More preferably 10-90/90-10/0-10,
Even more preferably 20-80/80-20/0-5,
Particularly 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 this embodiment is within the above range, it tends to be excellent in performance such as sensitivity and resolution in addition to roughness.

The radiation-sensitive composition of this embodiment may contain other resins as long as they do not impede the object of the present invention. Such other resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers or polymers containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units. These derivatives can be mentioned. The blending amount of these resins is appropriately adjusted depending on the type of component (A) used, but it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of component (A). It is not more than 5 parts by weight, more preferably not more than 5 parts by weight, particularly preferably 0 parts by weight.

[Method for forming resist pattern]
The method for forming a resist pattern in this embodiment includes forming a photoresist layer on a substrate using the resist composition or radiation-sensitive composition of this embodiment described above, and then applying radiation to a predetermined region of the photoresist layer. The process includes the steps of irradiating and developing. More specifically, it includes a step of forming a resist film on a substrate using the resist composition or 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 of forming the resist pattern is not particularly limited, and examples thereof include the following method. First, a resist film is formed by applying a resist composition or a radiation-sensitive composition onto a conventionally known substrate using a coating means such as spin coating, casting coating, or roll coating. The conventionally known substrate is not particularly limited, and includes, for example, a substrate for electronic components, a substrate on which a predetermined wiring pattern is formed, and the like. More specifically, examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. Examples of the material for the wiring pattern include copper, aluminum, nickel, and gold. Furthermore, an inorganic and/or organic film may be provided on the substrate, if necessary. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). Examples of organic films include organic antireflection films (organic BARC). The substrate may be surface treated with hexamethylene disilazane or the like.

Next, the substrate coated with the resist composition or radiation-sensitive composition is heated, if necessary. The heating conditions vary depending on the composition of the resist composition or the radiation-sensitive composition, but are preferably 20 to 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 any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected depending on 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 during exposure, it is preferable to heat the material after irradiation with radiation. The heating conditions vary depending on the composition of the resist composition or radiation-sensitive composition, but are preferably 20 to 250°C, more preferably 20 to 150°C.

Next, a predetermined resist pattern is formed by developing the exposed resist film with a developer. The developing solution has a solubility parameter (SP value) for the compound represented by formula (1) or formula (2) to be used or the resin obtained by using the compound represented by formula (1) or formula (2) as a monomer. ) is preferable, and polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents, hydrocarbon 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, and methyl ethyl ketone. , methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl 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, and ethyl-3 -ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, and the like.

Examples of alcoholic 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, Alcohols such as 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl Examples include glycol ether solvents such as ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol.

Examples of the ether solvent include dioxane, tetrahydrofuran, and the like, in addition to the above-mentioned glycol ether solvent.

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

Examples of the hydrocarbon solvent 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-mentioned solvents may be mixed together, or may be mixed with other solvents or water within the performance range. However, from the viewpoint of fully exhibiting the effects of the present invention, the water content of the entire developer is preferably less than 70% by mass, more preferably less than 50% by mass, and more preferably less than 30% by mass. It is more preferable that the content is less than 10% by mass, even more preferably that it is less than 10% by mass, and it is especially preferable that it 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, and 70% by mass or less, and more preferably 50% by mass or more and 100% by mass or less, based on the total amount of the developer. It is more preferably at least 90 mass% and at most 100 mass%, even more preferably at least 90 mass% and at most 100 mass%, and particularly preferably at least 95 mass% and at most 100 mass%.

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

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

The vapor pressure of the developer is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 20°C. When the vapor pressure of the developer is 5 kPa or less, evaporation of the developer on the substrate or in the developer cup is suppressed, and temperature uniformity within the wafer surface is improved, resulting in good dimensional uniformity within the wafer surface. There is a tendency to become

Examples of specific developing solutions 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, diisobutylketone, cyclohexanone, and methyl. Ketone solvents such as cyclohexanone, phenylacetone, 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-ethoxypropylene Ester solvents such as pionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate; n-propyl alcohol, isopropyl alcohol, n-butyl Alcohol solvents such as alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol; ethylene glycol , diethylene glycol, triethylene glycol, etc.; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, etc. Glycol ether solvents; ether solvents such as tetrahydrofuran; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene; Examples include aliphatic hydrocarbon solvents such as octane and decane.

Examples of specific developing solutions 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, diisobutylketone, cyclohexanone, and 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 - Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate; n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl Alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, and other alcohol-based solvents; ethylene glycol, diethylene glycol, triethylene glycol, and other glycol-based solvents; ethylene glycol monomethyl ether, propylene Glycol ether solvents such as glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol; N-methyl-2-pyrrolidone, N,N-dimethyl Examples include amide solvents such as acetamide and N,N-dimethylformamide; aromatic hydrocarbon solvents such as xylene; and aliphatic hydrocarbon solvents such as octane and decane.

An appropriate amount of a 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 silicone surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950. Publications, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Patent No. 5405720 , No. 5360692, No. 5529881, No. 5296330, No. 5436098, No. 5576143, No. 5294511, No. 5824451. Preferred are nonionic surfactants. The nonionic surfactant is not particularly limited, but is preferably a fluorine-based surfactant or a silicon-based surfactant.

The amount of surfactant used is usually 0.001 to 5% by weight, preferably 0.005 to 2% by weight, and more preferably 0.01 to 0.5% by weight, based on the total amount of the developer.

Development methods include, for example, a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and then developed by standing still for a certain period of time (paddle method). method), a method in which the developer is sprayed onto the surface of the substrate (spray method), and a method in which the developer is continued to be applied while scanning the developer application nozzle at a constant speed onto the substrate that is rotating at a constant speed (dynamic dispensing method). ) etc. can be applied. There is no particular restriction on the time for developing the pattern, but it is preferably 10 seconds to 90 seconds.

Furthermore, after the step of developing, a step of stopping the development may be carried out while replacing the solvent with another solvent.

After development, it is preferable to include a step of cleaning using a rinsing liquid containing an organic solvent.

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

Here, the monohydric alcohol used in the rinsing step after development includes linear, branched, and cyclic monohydric alcohols, and 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, etc. can be used, and particularly preferred monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-octanol, and the like. -Methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like.

A plurality of the above-mentioned components may be mixed together, or may be used in combination with an organic solvent other than those mentioned above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By controlling the water content in the rinse liquid to 10% by mass or less, better development characteristics tend to be obtained.

The vapor pressure of the rinse liquid 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, and 0.12 kPa or more and 3 kPa or less at 20°C. is even more preferable. When the vapor pressure of the rinsing liquid is 0.05 kPa or more and 5 kPa or less, the temperature uniformity within the wafer surface is further improved, and furthermore, swelling due to penetration of the rinsing liquid is further suppressed, resulting in uniform dimensions within the wafer surface. There is a tendency for sexual performance to improve.

An appropriate amount of a surfactant can also be added to the rinsing liquid.

In the rinsing step, the developed wafer is cleaned using a rinsing liquid containing the above organic solvent. The method of cleaning treatment is not particularly limited, but examples include a method of continuously applying a rinse liquid onto a substrate rotating at a constant speed (rotary coating method), and a method of immersing a substrate in a tank filled with a rinse liquid for a certain period of time. (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. Among them, the cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. It is preferable to remove the rinsing liquid from the substrate.

After forming a resist pattern, etching is performed to obtain a patterned wiring board. The etching method can be performed by a known method such as dry etching using plasma gas or wet etching using an alkaline solution, cupric chloride solution, ferric chloride solution, or the like.

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

The resist pattern remaining after etching can be removed with an organic solvent. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). Examples of the peeling method include a dipping method and a spray method. Furthermore, the wiring board on which the resist pattern is formed may be a multilayer wiring board, or may have small-diameter through holes.

The wiring board in this embodiment can also be formed by a method in which, after forming a resist pattern, metal is deposited in a vacuum and then the resist pattern is dissolved in a solution, that is, by a lift-off method.

[Lithography film-forming composition for lower layer film applications]
The lithography film forming composition for underlayer film applications (hereinafter also referred to as "lower film forming material") in this embodiment is a compound represented by the above formula (0) and a compound represented by the above formula (0). A resin obtained by using the compound represented by the above formula (1) as a monomer, more specifically 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 formula (2), and a compound represented by 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 this embodiment, from the viewpoint of applicability and quality stability, the content of the above substance is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and 50 to 100% by mass, based on the total mass of the solid component. It is more preferably % by mass, and particularly preferably 100% by mass.

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

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

Specific examples of solvents 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. , ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, and other ester solvents; methanol, ethanol, isopropanol, 1-ethoxy-2-propanol, and other alcohol solvents; toluene, xylene , aromatic hydrocarbons such as anisole, and the like. These solvents can be used alone or in combination of two or more.

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

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 preferably 200 to 5,000 parts by mass, based on 100 parts by mass of the total solid component. It is more preferable that the amount is 200 to 1000 parts by mass.

[Crosslinking agent]
The lower layer film forming material in this embodiment may contain a crosslinking agent as necessary from the viewpoint of suppressing intermixing. The crosslinking agent is not particularly limited, but for example, those described in International Publication No. 2013/024779 can be used.

Specific examples of crosslinking agents that can be used in this embodiment include phenolic compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and isocyanates. compounds, azide compounds, etc., but are not particularly limited thereto. These crosslinking agents can be used alone or in combination of two or more. Among these, benzoxazine compounds, epoxy compounds, or cyanate compounds are preferred, and benzoxazine compounds are more preferred from the viewpoint of improving etching resistance.

As the above-mentioned phenol compound, known ones can be used. For example, phenols include, in addition to phenol, alkylphenols such as cresols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalene diols, and bisphenols such as bisphenol A and bisphenol F. or polyfunctional phenol compounds such as phenol novolak and phenol aralkyl resin. Among these, aralkyl-type phenol resins are preferred from the viewpoint of heat resistance and solubility.

As the above-mentioned epoxy compound, known ones can be used, and it is selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, 3,3',5,5'-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl- 4,4'-dihydroxybiphenol, resorcinol, epoxidized products of divalent phenols such as naphthalene diols, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane , trivalent or higher phenols such as tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, phenol novolak, o-cresol novolak, etc. Epoxidized products, epoxidized products of co-condensed resins of dicyclopentadiene and phenols, epoxidized products of phenol aralkyl resins synthesized from phenols and paraxylylene dichloride, etc., biphenyls synthesized from phenols and bischloromethylbiphenyl, etc. Examples include epoxidized products of aralkyl-type phenol resins, and epoxidized products of naphthol aralkyl resins synthesized from naphthols, paraxylylene dichloride, and the like. These epoxy resins may be used alone or in combination of two or more. From the viewpoint of heat resistance and solubility, epoxy resins that are solid at room temperature are preferred, such as epoxy resins obtained from phenol aralkyl resins and biphenylaralkyl resins.

The cyanate compound is not particularly limited as long as it has two or more cyanate groups in one molecule, and any known compound can be used. In this embodiment, preferred cyanate compounds include those having a structure in which the hydroxyl group of a compound having two or more hydroxyl groups in one molecule is replaced with a cyanate group. Furthermore, the cyanate compound preferably has an aromatic group, and those having a structure in which the cyanate group is directly connected to the aromatic group can be suitably used. Examples of such cyanate compounds include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolak resin, dicyclopentadiene novolac resin, tetramethylbisphenol F, bisphenol A novolac resin, and bromine. bisphenol A, brominated phenol novolac resin, trifunctional phenol, tetrafunctional phenol, naphthalene type phenol, biphenyl type phenol, phenol aralkyl resin, biphenylaralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, alicyclic phenol, phosphorus Examples include those having a structure in which the hydroxyl group of the phenol contained therein is substituted with a cyanate group. These cyanate compounds may be used alone or in an appropriate combination of two or more. Moreover, the above-described cyanate compound may be in any form of monomer, oligomer, or resin.

The above amino compounds include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, , 3'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenyl Sulfide, 3,3'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis [4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy) ) phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-chlorophenyl)fluorene, 9, 9-bis(4-amino-3-fluorophenyl)fluorene, O-tolidine, m-tolidine, 4,4'-diaminobenzanilide, 2,2'-bis(trifluoromethyl)-4,4'-diamino Examples include biphenyl, 4-aminophenyl-4-aminobenzoate, and 2-(4-aminophenyl)-6-aminobenzoxazole. Furthermore, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Sulfone, 3,3'-diaminodiphenylsulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis [4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy) ) Aromatic amines such as phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diamino Bicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02 , 6] Decane, 1,3-bisaminomethylcyclohexane, alicyclic amines such as isophoronediamine, aliphatic amines such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylenetriamine, triethylenetetramine, etc. can be mentioned.

Examples of the benzoxazine compounds include P-d type benzoxazine obtained from bifunctional diamines and monofunctional phenols, F-a type benzoxazine obtained from monofunctional diamines and difunctional phenols, etc. It will be done.

Specific examples of the above-mentioned melamine compounds include hexamethylolmelamine, hexamethoxymethylmelamine, hexamethylolmelamine, a compound in which 1 to 6 methylol groups are methoxymethylated, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethyl Examples include compounds in which 1 to 6 of the methylol groups of melamine, hexamethylolmelamine are acyloxymethylated, or mixtures thereof.

Specific examples of the above-mentioned guanamine compounds include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which 1 to 4 methylol groups are methoxymethylated such as tetramethylolguanamine, or mixtures thereof, tetramethoxyethylguanamine, and tetraacyloxyguanamine. , a compound in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof.

Specific examples of the above-mentioned glycoluril compounds include, for example, tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 of the methylol groups of tetramethylol glycoluril are methoxymethylated, or mixtures thereof; Examples include compounds in which 1 to 4 of the methylol groups of tetramethylol glycoluril are acyloxymethylated, or mixtures thereof.

Specific examples of the above-mentioned urea compounds include, for example, tetramethylolurea, tetramethoxymethylurea, compounds in which 1 to 4 methylol groups are methoxymethylated such as tetramethylolurea, or mixtures thereof, and tetramethoxyethylurea.

Further, in this embodiment, from the viewpoint of improving crosslinking properties, a crosslinking agent having at least one allyl group may be used. Specific examples of crosslinking agents having at least one allyl group include 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2 -Bis(3-allyl-4-hydroxyphenyl)propane, bis(3-allyl-4-hydroxyphenyl)sulfone, bis(3-allyl-4-hydroxyphenyl)sulfide, bis(3-allyl-4-hydroxyphenyl) ) ethers and other allylphenols, 2,2-bis(3-allyl-4-cyanatophenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3 -Allyl-4-cyanatophenyl) propane, bis(3-allyl-4-cyanatocyphenyl) sulfone, bis(3-allyl-4-cyanatophenyl) sulfide, bis(3-allyl-4-cyanatophenyl) ) Allyl cyanates such as ethers, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol allyl ether, etc., but are limited to these examples. It's not a thing. These may be used alone or in a mixture of two or more. Among these, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3-allyl-4-hydroxyphenyl) ) Propane, bis(3-allyl-4-hydroxyphenyl) sulfone, bis(3-allyl-4-hydroxyphenyl) sulfide, bis(3-allyl-4-hydroxyphenyl) ether and other allylphenols are preferred. .

The content of the crosslinking agent in the lower layer film forming material is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, even more preferably 10% by mass, based on the total mass of the solid components. ~40% by mass. By setting the content of the crosslinking agent within the above range, the occurrence of mixing phenomenon with the resist layer tends to be suppressed, and the antireflection effect tends to be enhanced and the film forming property after crosslinking tends to be enhanced. .

[Crosslinking accelerator]
A crosslinking accelerator for accelerating crosslinking and curing reactions can be used in the lower layer film forming material of this embodiment, if necessary.

The crosslinking accelerator is not particularly limited as long as it promotes crosslinking and curing reactions, and examples thereof include amines, imidazoles, organic phosphines, Lewis acids, and the like. These crosslinking accelerators can be used alone or in combination of two or more. Among these, imidazoles or organic phosphines are preferred, and imidazoles are more preferred from the viewpoint of lowering the crosslinking temperature.

Examples of the crosslinking accelerator include, but are not limited to, 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminoethanol), and the like. Tertiary amines such as methyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5- Imidazoles such as triphenylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium/tetraphenylborate, tetraphenylphosphonium/ethyltriphenylborate, tetrabutyl Examples include tetra-substituted phosphonium/tetra-substituted borates such as phosphonium/tetrabutylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole/tetraphenylborate, and N-methylmorpholine/tetraphenylborate.

The content of the crosslinking accelerator is usually preferably 0.1 to 10% by mass based on the total mass of the solid component, and more preferably 0.1 to 5% by mass from the viewpoint of ease of control and economic efficiency. mass%, more preferably 0.1 to 3 mass%

[Radical polymerization initiator]
A radical polymerization initiator can be added to the lower layer film-forming material of this embodiment, if necessary. The radical polymerization initiator may be a photopolymerization initiator that starts radical polymerization with light, or a thermal polymerization initiator that starts radical polymerization with heat. The radical polymerization initiator may be, for example, at least one selected from the group consisting of ketone photopolymerization initiators, organic peroxide polymerization initiators, and azo polymerization initiators.

Such radical polymerization initiators are not particularly limited, and conventionally used ones can be appropriately employed. For example, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2 -Methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methylpropan-1-one, 2 , 4,6-trimethylbenzoyl-diphenyl-phosphine oxide, ketone photoinitiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide oxide, methyl acetoacetate peroxide, acetylacetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane oxy)-cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxy) oxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide oxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, Di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide oxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butyl) cyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, Di(3-methyl-3-methoxybutyl) peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-tetramethyl Butyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate , t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy) Hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy Oxyisopropyl monocarbonate, t-butyl peroxyisobutyrate, t-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethohexanoate, t-butyl peroxylaurate, t- Butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxybenzoate) oxy)isophthalate, 2,5-dimethyl-2,5-bis(m-tolylperoxy)hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-Butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,3-dimethyl-2,3-diphenylbutane, etc. Examples include organic peroxide polymerization initiators.

Also, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( 2-Methylpropionamidine) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine] Dihydrido chloride, 2,2'-azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydro Chloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propionamidine] dihydrochloride, 2,2'-azobis[N-(2-hydroxyethyl)-2-methylpropionamidine] dihydrochloride , 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride , 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3, 4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydro Chloride, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2- yl)propane], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N -[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methyl propionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), Also included are azo polymerization initiators such as 4,4'-azobis(4-cyanopentanoic acid) and 2,2'-azobis[2-(hydroxymethyl)propionitrile]. As the radical polymerization initiator in this embodiment, one type of these may be used alone or two or more types may be used in combination, and other known polymerization initiators may be further used in combination.

The content of the radical polymerization initiator may be any stoichiometrically necessary amount, but it is preferably 0.05 to 25% by mass, preferably 0.1 to 10% by mass of the total weight of the solid components. It is more preferable that When the content of the radical polymerization initiator is 0.05% by mass or more, insufficient curing tends to be prevented; on the other hand, when the content of the radical polymerization initiator is 25% by mass or less In this case, it tends to be possible to prevent the long-term storage stability of the lower layer film-forming material from being impaired at room temperature.

[Acid generator]
The lower layer film-forming material in this embodiment may contain an acid generator as necessary, from the viewpoint of further promoting the crosslinking reaction due to heat. As acid generators, there are known ones that generate acids by thermal decomposition, those that generate acids by light irradiation, etc., and any of them can be used. As the acid generator, for example, those described in International Publication No. 2013/024779 can be used.

The content of the acid generator in the lower film forming material is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass of the total mass of the solid components. . By setting the content of the acid generator within the above range, the amount of acid generated tends to increase and the crosslinking reaction tends to be enhanced, and the occurrence of mixing phenomenon with the resist layer tends to be suppressed.

[Basic compound]
The lower layer film forming material in this embodiment may contain a basic compound from the viewpoint of improving storage stability.

The basic compound serves as a quencher for the acid to prevent the trace amount of acid generated from the acid generator from proceeding with the crosslinking reaction. Such basic compounds are not particularly limited, but include, for example, those described in International Publication No. 2013/024779.

The content of the basic compound in the lower layer film forming material is not particularly limited, but is preferably 0.001 to 2% by mass, more preferably 0.01 to 1% by mass, based on the total mass of the solid components. . By setting the content of the basic compound within the above range, storage stability tends to be improved without excessively impairing the crosslinking reaction.

[Other additives]
Further, the lower layer film forming material in this 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 resins, naphthol-modified resins, phenol-modified naphthalene resins; polyhydroxystyrene, dicyclopentadiene resins, (meth)acrylates, dimethacrylates, trimethacrylates, and tetramethacrylates. Resins containing naphthalene rings such as methacrylate, vinylnaphthalene, and polyacenaphthylene, biphenyl rings such as phenanthrenequinone and fluorene, and heterocycles having heteroatoms such as thiophene and indene, and resins containing no aromatic rings; rosin resins; Examples include resins or compounds containing an alicyclic structure such as cyclodextrin, adamantane (poly)ol, tricyclodecane (poly)ol, and derivatives thereof, but are not particularly limited thereto. Furthermore, the lower layer film forming material in this embodiment may contain known additives. Known additives include, but are not limited to, thermal and/or photocuring catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photocuring resins, dyes, and pigments. , thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants, and the like.

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

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

Further, in the circuit pattern forming method of the present embodiment, a lower layer film is formed on a substrate using the above composition, an intermediate layer film is formed on the lower layer film using a resist intermediate layer film material, and the intermediate layer film is formed on the lower layer film using a resist intermediate layer film material. forming at least one photoresist layer on the film;
irradiating a predetermined region of the photoresist layer with radiation and developing it 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. It includes a step of forming a pattern.

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

The method for forming the lower layer film for lithography in this embodiment is not particularly limited as long as it is formed from the lower layer film forming material of this embodiment, and any known method can be applied. For example, the lower layer film material of this embodiment is applied onto a substrate by a known coating method such as spin coating or screen printing, or by a printing method, and then removed by volatilizing the organic solvent, and then cross-linked by a known method. The underlayer film for lithography of this embodiment can be formed by curing. Examples of the crosslinking method include methods such as thermosetting and photocuring.

When forming the lower layer film, baking is preferably performed in order to suppress the occurrence of a mixing phenomenon with the upper layer resist and to promote the crosslinking 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 to 400°C. The baking time is also not particularly limited, but is preferably within a range of 10 to 300 seconds. Note that the thickness of the lower layer film can be appropriately selected depending on the required performance and is not particularly limited, but it is usually preferably about 30 to 20,000 nm, more preferably 50 to 15,000 nm.

After producing the lower layer film, in the case of a two-layer process, a silicon-containing resist layer or a single-layer resist made of ordinary hydrocarbon is applied on top of it, and in the case of a three-layer process, a silicon-containing intermediate layer is placed on top of it, and then a silicon-containing intermediate layer is placed on top of it in the case of a three-layer process. It is preferable to fabricate a single resist layer containing no silicon. In this case, known photoresist materials can be used to form this resist layer.

After the lower layer film is formed on the substrate, in the case of a two-layer process, a silicon-containing resist layer or a single layer resist made of ordinary hydrocarbon can be formed on the lower layer film. In the case of a three-layer process, a silicon-containing intermediate layer can be formed on the lower layer film, and a single-layer resist layer that does not contain silicon can be further 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 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, known polymers used in this type of resist material can be used.

As silicon-containing interlayer for three-layer processes, polysilsesquioxane-based interlayers are preferably used. Reflection tends to be effectively suppressed by providing the intermediate layer with the effect of an antireflection film. For example, in a 193 nm exposure process, if a material containing many aromatic groups and high substrate etching resistance is used as the lower layer film, the k value will increase and the substrate reflection will tend to increase, but it is necessary to suppress the reflection with an intermediate layer. Accordingly, substrate reflection can be reduced to 0.5% or less. Intermediate layers having such an antireflection effect are not limited to the following, but for 193 nm exposure, polysilsesquies cross-linked with acid or heat, into which a phenyl group or a light-absorbing group having a silicon-silicon bond are introduced, can be used. Oxane is preferably used.

Further, 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 produced by a CVD method that is highly effective as an antireflection film. Generally, it is easier and more cost-effective to form the intermediate layer by a wet process such as a spin coating method or screen printing than by a CVD method. Note that the upper layer resist in the three-layer process may be either positive type or negative type, and may be the same as the commonly used single layer resist.

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

When forming a resist layer using the above-mentioned photoresist material, a wet process such as a spin coating method or screen printing is preferably used as in the case of forming the above-mentioned lower layer film. Further, after applying the resist material by spin coating or the like, prebaking is usually performed, and this prebaking is preferably performed at 80 to 180° C. for 10 to 300 seconds. Thereafter, a resist pattern can be obtained by performing exposure, post-exposure bake (PEB), and development according to a conventional method. Note that the thickness of the resist film is not particularly limited, but is generally preferably 30 to 500 nm, more preferably 50 to 400 nm.

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

The resist pattern formed by the method described above has pattern collapse suppressed by the lower layer film. Therefore, by using the lower layer film in this embodiment, a finer pattern can be obtained, and the amount of exposure necessary to obtain 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, it is also possible to add inert gases such as He and Ar, and CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ , and H ₂ gases. Further, gas etching can also be performed using only CO, CO ₂ , NH ₃ , N ₂ , NO ₂ , or H ₂ gas 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 gas etching 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 fluorocarbon-based gas using a resist pattern as a mask. Thereafter, the lower layer film can be processed by performing, for example, oxygen gas etching using the intermediate layer pattern as a mask as described above.

Here, when forming an inorganic hard mask intermediate layer film as an intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) is formed by a CVD method, an ALD method, or the like. Although the method for forming the nitride film is not limited to the following, for example, the methods described in JP-A No. 2002-334869 (Patent Document 6) and WO 2004/066377 (Patent Document 7) can be used. Although it is possible to form a photoresist film directly on such an intermediate layer film, it is also possible to form an organic anti-reflection coating (BARC) on the intermediate layer film by spin coating, and then form a photoresist film on it. You may.

As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. There is a tendency that reflection can be effectively suppressed by giving the resist intermediate layer film the effect of an antireflection film. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, but are described, for example, in JP-A No. 2007-226170 (Patent Document 8) and JP-A No. 2007-226204 (Patent Document 9). You can use the one given.

In addition, the next substrate etching can be carried out by a conventional method. For example, if the substrate is SiO2 or SiN, etching using fluorocarbon gas as the main ingredient, or using chlorine or bromine gas for p-Si, Al, or W. Etching can be performed mainly using When etching a substrate with a fluorocarbon-based gas, the silicon-containing resist in the two-layer resist process and the silicon-containing intermediate layer in the three-layer process are peeled off at the same time as the substrate is processed. On the other hand, when the substrate is etched with chlorine-based or bromine-based gas, the silicon-containing resist layer or silicon-containing intermediate layer is removed separately, and generally dry etching removal using fluorocarbon-based gas is performed after substrate processing. .

The lower layer film in this embodiment is characterized by excellent etching resistance of the substrate. Note that the substrate can be appropriately selected and used from known substrates, and examples include, but are not limited to, Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, etc. It will be done. Further, the substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). Such films to be processed include various low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and their stoppers. Examples include membranes, etc., and those made of a material different from that of the base material (support) are usually used. Note that the thickness of the substrate to be processed or the film to be processed is not particularly limited, but it is usually preferably about 50 to 10,000 nm, more preferably 75 to 5,000 nm.

[Resist permanent film]
Note that a permanent resist film can also be produced using the above composition.The permanent resist film formed by applying the above composition is a permanent film that remains in the final product after forming a resist pattern as necessary. It is suitable as Specific examples of permanent films include solder resists, packaging materials, underfill materials, package adhesive layers for circuit elements, and adhesive layers between integrated circuit elements and circuit boards in the semiconductor device field, thin film transistor protective films, and thin film transistor protective films in the thin display field. Examples include liquid crystal color filter protective films, black matrices, spacers, etc. In particular, the permanent film made of the above composition has excellent heat resistance and moisture resistance, and also has the very excellent advantage of being less likely to be contaminated by sublimation components. Particularly in display materials, the material has high sensitivity, high heat resistance, and moisture absorption reliability with little deterioration of image quality due to important contamination.

When using the above composition for resist permanent film applications, in addition to the curing agent, various additives such as other resins, surfactants, dyes, fillers, crosslinking agents, and dissolution promoters may be added as necessary. By dissolving it in an organic solvent, it can be made into a composition for resist permanent film.

The film forming composition for lithography and the composition for resist permanent film can be prepared by blending the above components and mixing them using a stirrer or the like. In addition, if the composition for resist underlayer film or the composition for resist permanent film contains fillers or pigments, they may be adjusted by dispersing or mixing using a dispersing device such as a dissolver, homogenizer, or three-roll mill. I can do it.

Hereinafter, the present embodiment will be described in more detail with reference to synthesis examples, synthesis examples, working examples, and comparative examples, but the present embodiment is not limited to these examples in any way.

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

(molecular weight)
The molecular weight of the compound was measured by LC-MS analysis using Acquity UPLC/MALDI-Synapt HDMS manufactured by Water.
In addition, gel permeation chromatography (GPC) analysis was performed under the following conditions to determine the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw/Mn) in terms of polystyrene.
Equipment: Shodex GPC-101 type (manufactured by Showa Denko K.K.)
Column: KF-80M x 3
Eluent: THF 1mL/min
Temperature: 40℃

(Solubility)
At 23°C, the compound was dissolved in propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethyl urea (TMU) to a 10% by mass solution. The results after one week 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 was confirmed by 1H-NMR measurement using Bruker's "Advance 600II spectrometer" under the following conditions.
Frequency: 400MHz
Solvent: d6-DMSO
Internal standard: TMS
Measurement temperature: 23℃

<Synthesis Example 1> Synthesis of XBisN-1 In a container with an internal volume of 100 mL equipped with a stirrer, a cooling tube, and a burette, 3.20 g (20 mmol) of 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich) and 4-biphenylcarboxylic acid were added. 1.82 g (10 mmol) of aldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to 30 mL of methyl isobutyl ketone, 5 mL of 95% sulfuric acid was added, and the reaction solution was stirred at 100° C. for 6 hours to carry out the reaction. Next, the reaction solution was concentrated, 50 g of pure water was added to precipitate the reaction product, and after cooling to room temperature, it was filtered and separated. The obtained solid was filtered and dried, and then separated and purified by column chromatography to obtain 3.05 g of the target compound represented by the following formula. It was confirmed by 400MHz- ¹ H-NMR that it had the chemical structure of the following formula.
^1H -NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.7 (2H, O-H), 7.2-8.5 (19H, Ph-H), 6.6 (1H, C-H)
It was confirmed that the substitution position of 2,6-naphthalenediol was at the 1st position because the proton signals at the 3rd and 4th positions were a doublet.

（ＸＢｉｓＮ－１）

(XBisN-1)

<Synthesis Example 2> Synthesis of BisF-1 A container with an internal volume of 200 mL equipped with a stirrer, a cooling tube, and a buret 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 were charged, and p-toluenesulfone was added. A reaction solution was prepared by adding 3.9 g (21 mmol) of acid (reagent manufactured by Kanto Kagaku Co., Ltd.). 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, and after cooling to room temperature, it was filtered and separated. After drying the solid obtained by filtration, it was separated and purified by column chromatography to obtain 5.8 g of the target compound (BisF-1) represented by the following formula.
In addition, the following peaks were found by 400MHz- ¹ H-NMR, and it was confirmed that it had the chemical structure of the following formula.
^1H -NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.4 (4H, O-H), 6.8-7.8 (22H, Ph-H), 6.2 (1H, C-H)
The molecular weight of the obtained compound was measured by the above method and was found to be 536.

（ＢｉｓＦ－１）

(BisF-1)

<Synthesis Example 1-1> Synthesis of Al-XBisN-1 9.8 g (21 mmol) of the compound represented by the above formula (XBisN-1) and potassium carbonate were placed in a 100 mL container equipped with a stirrer, a cooling tube, and a burette. 6.2 g (45 mmol) was added to 100 mL of acetone, and then 5.4 (45 mmol) g of allyl bromide and 2.0 g of 10-crown-6 were added, and the resulting reaction solution was refluxed. The reaction was carried out by stirring for 7 hours. Next, solid matter was removed from the reaction solution by filtration, cooled in an ice bath, and the reaction solution was concentrated to precipitate solid matter. The precipitated solid was filtered and dried, and then separated and purified by column chromatography to obtain 4.0 g of the target compound represented by the following formula (Al-XBisN-1).
It was confirmed by 400MHz- ¹ H-NMR that it had the chemical structure of the following formula (Al-XBisN-1).
^1H -NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2 to 7.8 (19H, Ph-H), 6.7 (1H, CH), 6.1 (2H, -CH=CH ₂ ), 5.4 to 5.5 (4H, -CH=CH ₂ )
The molecular weight of the obtained compound was measured by the above method and was found to be 546.

（Ａｌ－ＸＢｉｓＮ－１）

(Al-XBisN-1)

<Synthesis Example 2-1> Synthesis of Al-BisF-1 Synthesis was carried out except that the compound represented by the above formula (BisF-1) was used instead of the compound represented by the above formula (XBisN-1). The reaction was carried out in the same manner as in Example 1 to obtain 3.0 g of the target compound represented by the following formula (Al-BisF-1).
It was confirmed by 400MHz- ¹ H-NMR that it had the chemical structure of the following formula (Al-BisF-1).
^1H -NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8 to 7.8 (22H, Ph-H), 6.2 (1H, CH), 6.1 (4H, -CH=CH ₂ ), 5.4 to 5.5 (8H, -CH=CH ₂ ),
The molecular weight of the obtained compound was measured by the above method and was found to be 872.

（Ａｌ－ＢｉｓＦ－１）

(Al-BisF-1)

<Synthesis Example 1-2> Synthesis of AlOH-XBisN-1 6.1 g (11 mmol) of the compound represented by the above formula (Al-XBisN-1) was placed in a 100 mL container equipped with a stirrer, a cooling tube, and a burette. was added to 6.0 mL, and the reaction solution was stirred at 130° C. for 6 hours, and 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 obtained solid was filtered and dried, and then separated and purified by column chromatography to obtain 0.90 g of the target compound represented by the following formula.
It was confirmed by 400MHz- ¹ H-NMR that it had the chemical structure of the following formula.
^1H -NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.6 (2H, O-H), 7.3-8.5 (17H, Ph-H), 6.6 (1H, C-H), 5.9 (2H, -CH= CH ₂ ), 4.9 (4H, -CH=CH ₂ ), 3.8 (4H, -CH ₂ -)
The molecular weight of the obtained compound was measured by the above method and was found to be 546.

（ＡｌＯＨ－ＸＢｉｓＮ－１）

(AlOH-XBisN-1)

The thermal decomposition temperature of the obtained compound was 400°C, the glass transition temperature was 211°C, and it was confirmed that the compound had high heat resistance.

<Synthesis Example 2-2> Synthesis of AlOH-BisF-1 6.1 g (9 mmol) of the compound represented by the above formula (Al-BisF-1) was placed in a 100 mL container equipped with a stirrer, a cooling tube, and a burette. was added to 6.0 mL, and the reaction solution was stirred at 130° C. for 6 hours, and 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 obtained solid was filtered and dried, and then separated and purified by column chromatography to obtain 1.05 g of the target compound represented by the following formula.
It was confirmed by 400MHz- ¹ H-NMR that it had the chemical structure of the following formula.
^1H -NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.4 (4H, O-H), 6.8 to 7.8 (18H, Ph-H), 6.2 (1H, C-H), 5.9 (4H, -CH= CH ₂ ), 4.9 (8H, -CH=CH ₂ ), 3.8 (8H, -CH ₂ -)
The molecular weight of the obtained compound was measured by the above method and was found to be 696.

（ＡｌＯＨ－ＢｉｓＦ－１）

(AlOH-BisF-1)

The thermal decomposition temperature was 390°C, the glass transition temperature was 200°C, and it was confirmed that it had high heat resistance.

(Synthesis examples 3 to 10)
The raw materials of Synthesis Example 1, 2,6-naphthalenediol and 4-biphenylcarboxaldehyde, were changed as shown in Raw Materials 1 and 2 in Table 1, and the rest was carried out in the same manner as Synthesis Example 1 to obtain each target product. .
Each was identified by 1H-NMR (Table 2).

（ＸＢｉｓＮ－２）

(XBisN-2)

（ＸＢｉｓＮ－３）

(XBisN-3)

（ＸＢｉｓＮ－４）

(XBisN-4)

（ＸＢｉｓＮ－５）

(XBisN-5)

（ＸＢｉｓＮ－６）

(XBisN-6)

（ＸＢｉｓＮ－７）

(XBisN-7)

（ＸＢｉｓＮ－８）

(XBisN-8)

（ＸＢｉｓＮ－９）

(XBisN-9)

(Synthesis Examples 11 to 13)
The raw materials 2,6-naphthalenediol and 4-biphenylcarboxaldehyde in Synthesis Example 1 were changed as shown in Raw Materials 1 and 2 in Table 3, and 1.5 mL of water, 73 mg (0.35 mmol) of dodecyl mercaptan, and 37% 2.3 g (22 mmol) of hydrochloric acid was added, and the reaction temperature was changed to 55° C., but otherwise the same procedure as in Synthesis Example 1 was carried out to obtain each desired product.
Each was identified by 1H-NMR.

（Ｐ－５）

(P-5)

（Ｐ－６）

(P-6)

（Ｐ－７）

(P-7)

(Synthesis Examples 3-1 to 13-1)
The compound represented by the above formula (XBisN-1), which is the raw material for Synthesis Example 1-1, was changed as shown in Raw Material 1 in Table 5, and the synthesis was carried out under the same conditions as in Synthesis Example 1-1. They each obtained their desired objects. The structure of each compound was identified by confirming the molecular weight using 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(Synthesis Examples 3-2 to 13-2)
The compound represented by the above formula (Al-XBisN-1), which is the raw material for Synthesis Example 1-2, was changed as shown in Raw Material 1 in Table 5, and the other conditions were the same as in Synthesis Example 1-2. Synthesis was performed and the desired products were obtained. The structure of each compound was identified by confirming the molecular weight using 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

（Ａｌ－ＸＢｉｓＮ－２）

(Al-XBisN-2)

（ＡｌＯＨ－ＸＢｉｓＮ－２）

(AlOH-XBisN-2)

（Ａｌ－ＸＢｉｓＮ－３）

(Al-XBisN-3)

（ＡｌＯＨ－ＸＢｉｓＮ－３）

(AlOH-XBisN-3)

（Ａｌ－ＸＢｉｓＮ－４）

(Al-XBisN-4)

（ＡｌＯＨ－ＸＢｉｓＮ－４）

(AlOH-XBisN-4)

（Ａｌ－ＸＢｉｓＮ－５）

(Al-XBisN-5)

（ＡｌＯＨ－ＸＢｉｓＮ－５）

(AlOH-XBisN-5)

（Ａｌ－ＸＢｉｓＮ－６）

(Al-XBisN-6)

（ＡｌＯＨ－ＸＢｉｓＮ－６）

(AlOH-XBisN-6)

（Ａｌ－ＸＢｉｓＮ－７）

(Al-XBisN-7)

（ＡｌＯＨ－ＸＢｉｓＮ－７）

(AlOH-XBisN-7)

（Ａｌ－ＸＢｉｓＮ－８）

(Al-XBisN-8)

（ＡｌＯＨ－ＸＢｉｓＮ－８）

(AlOH-XBisN-8)

（Ａｌ－ＸＢｉｓＮ－９）

(Al-XBisN-9)

（ＡｌＯＨ－ＸＢｉｓＮ－９）

(AlOH-XBisN-9)

（Ａｌ－Ｐ－５）

(Al-P-5)

（ＡｌＯＨ－Ｐ－５）

(AlOH-P-5)

（Ａｌ－Ｐ－６）

(Al-P-6)

（ＡｌＯＨ－Ｐ－６）

(AlOH-P-6)

（Ａｌ－Ｐ－７）

(Al-P-7)

（ＡｌＯＨ－Ｐ－７）

(AlOH-P-7)

(Synthesis Example 14) Synthesis of Resin (R1-XBisN-1) A four-necked flask with an internal volume of 1 L, which was equipped with a Dimroth condenser, a thermometer, and a stirring blade, and which could be bottomed out was prepared. Into this four-necked flask, in a nitrogen stream, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound obtained in Synthesis Example 1 (XBisN-1) and 21.0 g of a 40% by mass formalin aqueous solution (formaldehyde 280 mmol (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 the mixture was reacted for 7 hours under normal pressure and reflux at 100°C. Thereafter, 180.0 g of ortho-xylene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added as a diluting solvent to the reaction solution, and after standing still, the lower aqueous phase was removed. Furthermore, 34.1 g of brown solid resin (R1-XBisN-1) was obtained by neutralizing and washing with water, and distilling off ortho-xylene under reduced pressure.

The obtained resin (R1-XBisN-1) had Mn: 1975, Mw: 3650, and Mw/Mn: 1.84.

(Synthesis Example 15) Synthesis of Resin (R2-XBisN-1) A four-necked flask with an internal volume of 1 L, which was equipped with a Dimroth condenser, a thermometer, and a stirring blade, and which could be bottomed out was prepared. In this four-necked flask, in a nitrogen stream, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound obtained in Synthesis Example 1 (XBisN-1) and 50.9 g (280 mmol, (manufactured by Mitsubishi Gas Chemical Co., Ltd.), anisole (manufactured by Kanto Chemical Co., Ltd.), 100 mL, and oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) 10 mL were charged and reacted for 7 hours under normal pressure while refluxing at 100°C. I let it happen. Thereafter, 180.0 g of ortho-xylene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added as a diluting solvent to the reaction solution, and after standing still, the lower aqueous phase was removed. Further, neutralization and water washing were performed, and the organic phase solvent and unreacted 4-biphenylaldehyde were distilled off under reduced pressure to obtain 34.7 g of a brown solid resin (R2-XBisN-1).

The obtained resin (R2-XBisN-1) had Mn: 1610, Mw: 2567, and Mw/Mn: 1.59.
<Synthesis Example 14-1> Synthesis of Al-R1-XBisN-1 30 g of the resin (R1-XBisN-1) represented by the above formula and potassium carbonate were placed in a 500 ml container equipped with a stirrer, a cooling tube, and a burette. 29.6 g (214 mmol) were added to 100 ml dimethylformamide, 13.12 g (108 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the above crystals, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were charged into a 100 ml container equipped with a stirrer, a cooling tube, and a burette, and the reaction solution was stirred under reflux for 4 hours to carry out the reaction. . Thereafter, the reaction solution was cooled in an ice bath, the reaction solution was concentrated, and the precipitated solid was filtered and dried to obtain 26.5 g of a brown solid resin (Al-R1-XBisN-1).

The obtained resin (Al-R1-XBisN-1) had Mn: 2076, Mw: 3540, and Mw/Mn:.
<Synthesis Example 14-2> Synthesis of AlOH-R1-XBisN-1 20.0 g of the resin represented by the above formula (R1-XBisN-1) and 12.8 g of vinylbenzyl chloride (trade name: CMS-P; manufactured by Seimi Chemical Co., Ltd.) was added to 200 ml of dimethylformamide, heated to 50°C and stirred, and 28 wt% sodium methoxide (methanol solution) 16 .0 g was added from the dropping funnel over 20 minutes, and the reaction solution was stirred at 50° C. for 1 hour to carry out the reaction. Next, 3.2 g of 28 wt% sodium methoxide (methanol solution) was added, the reaction mixture was heated to 60°C and stirred for 5 hours, and 2.4 g of 85 wt% phosphoric acid was added, stirred for 10 minutes, and then heated to 40°C. Cool, drop the reaction solution into pure water, filter the precipitated solids, dry, cool to 50°C, drop the reaction solution into pure water, filter the precipitated solids, After drying, 27.2 g of a gray solid resin represented by (AlOH-R1-XBisN-1) was obtained.

The obtained resin (AlOH-R1-XBisN-1) had Mn: 2121, Mw: 3640, and Mw/Mn:.

<Synthesis Example 15-1> Synthesis of Al-R2-XBisN-1 30 g of the above resin (R2-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were placed in a 500 ml container equipped with a stirrer, a cooling tube, and a burette. ) was added to 100 ml of dimethylformamide, 13.12 g (108 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the above crystals, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were charged into a 100 ml container equipped with a stirrer, a cooling tube, and a burette, and the reaction solution was stirred under reflux for 4 hours to carry out the reaction. . Thereafter, it was cooled in an ice bath, the reaction solution was concentrated, and the precipitated solid was filtered and dried to obtain 22.3 g of a brown solid resin (Al-R2-XBisN-1).

The obtained resin (Al-R2-XBisN-1) had Mn: 2116, Mw: 3160, and Mw/Mn: 1.62.

<Synthesis Example 15-2> Synthesis of AlOH-R2-XBisN-1 Instead of the above formula (Al-R1-XBisN-1) obtained in Synthesis Example 14-1, The reaction was carried out in the same manner as in Synthesis Example 14-2 except that 40.5 g of the compound represented by the above formula (Al-R2-XBisN-1) was used. ) was obtained.

The obtained resin (AlOH-R2-XBisN-1) had Mn: 2244, Mw: 3215, and Mw/Mn:.

<Synthesis comparative example 1>
A four-necked flask with an internal volume of 10 L, which was equipped with a Dimroth condenser, a thermometer, and a stirring blade, was prepared. In a nitrogen stream, 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.1 kg of a 40% by mass formalin aqueous solution (28 mol as formaldehyde, manufactured by Mitsubishi Gas Chemical Co., Ltd.) were placed in this four-necked flask. ) and 0.97 mL of 98% by mass sulfuric acid (manufactured by Kanto Kagaku Co., Ltd.) were charged, and the mixture was reacted for 7 hours while refluxing at 100° C. under normal pressure. Thereafter, 1.8 kg of ethylbenzene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution as a diluting solvent, and after standing still, the lower aqueous phase was removed. Further, the mixture was neutralized and washed with water, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of dimethylnaphthalene formaldehyde resin as a pale brown solid.
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. 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of p-toluenesulfonic acid were charged into this four-necked flask under a nitrogen stream, and the temperature was raised to 190°C. After heating for an hour, it was stirred. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, the temperature was raised to 220° C., and the mixture was reacted for 2 hours. After diluting the solvent, it was neutralized and washed with water, and the solvent was removed under reduced pressure to obtain 126.1 g of a modified resin (CR-1) as a dark brown solid.
The obtained resin (CR-1) had Mn: 885, Mw: 2220, and Mw/Mn: 4.17. Further, the carbon concentration was 89.1% by mass, and the oxygen concentration was 4.5% by mass.

[Examples 1-1 to 15-2, Comparative Example 1]
A solubility test was conducted using the compounds or resins described in Synthesis Examples 1-1 to 15-2 and CR-1 described in Synthesis Comparative Example 1. The results are shown in Table 6.

In addition, lower layer film forming materials for lithography having the compositions shown in Table 6 were prepared. Next, these materials for forming a lower layer film for lithography were spin-coated onto a silicon substrate, and then baked at 240° C. for 60 seconds and further at 400° C. for 120 seconds to form a lower layer film with a thickness of 200 nm. The following acid generators, crosslinking agents, and organic solvents were used.
・Acid generator: Midori Kagaku Co., Ltd. ditertiary butyl diphenyliodonium nonafluoromethanesulfonate (DTDPI)
・Crosslinking agent: Nikalac MX270 (Nicalac) manufactured by Sanwa Chemical Co., Ltd.
・Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA)
・Novolac: PSM4357 manufactured by Gunei Chemical Co., Ltd.

In addition, lower layer film forming materials for lithography having the compositions shown in Table 7 below were prepared. Next, these materials for forming a lower layer film for lithography were spin-coated onto a silicon substrate, and then baked at 110° C. for 60 seconds to remove the solvent from the coating film, and then exposed using a high-pressure mercury lamp at a cumulative exposure dose of 600 mj. /cm ² and curing for 20 seconds for an irradiation time to produce a lower layer film with a thickness of 200 nm. The following photoacid generator, crosslinking agent, and organic solvent were used.

・Radical polymerization initiator: IRGACURE184 manufactured by BASF
・Crosslinking agent:
Mitsubishi Gas Chemical Diallyl bisphenol A cyanate (DABPA-CN)
Konishi Chemical Industry Co., Ltd. diallyl bisphenol A (BPA-CA)
Konishi Chemical Industry Benzoxazine (BF-BXZ)
Nippon Kayaku biphenylaralkyl epoxy resin (NC-3000-L)
・Organic solvent:
Propylene glycol monomethyl ether acetate acetate (PGMEA)

The structure of the above crosslinking agent is shown by the following formula.

（ＤＡＢＰＡ－ＣＮ）

(DABPA-CN)

（ＢＰＡ－ＣＡ）

(BPA-CA)

（ＢＦ－ＢＸＺ）

(BF-BXZ)

（上記式中、ｎは１～４の整数である。）
（ＮＣ－３０００－Ｌ）

(In the above formula, n is an integer from 1 to 4.)
(NC-3000-L)

[Etching resistance]
An etching test was conducted under the conditions shown below to evaluate etching resistance. The evaluation results are shown in Tables 8 and 9.

[Etching test]
Etching device: RIE-10NR manufactured by Samco International Co., Ltd.
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50:5:5 (sccm)

Etching resistance was evaluated using the following procedure.
First, a lower layer film of novolac was prepared under the same conditions as in Example 1, except that novolac (PSM4357, manufactured by Gunei Chemical Co., Ltd.) was used instead of the compound (AlOH-XBisN-1). Then, the above etching test was performed on this novolac lower layer film, and the etching rate at that time was measured.
Next, the above-mentioned etching test was similarly performed on the lower layer films of Examples 1-1 and 1-2 and Comparative Example 1, and the etching rate was measured. Then, the etching resistance was evaluated using the following evaluation criteria based on the etching rate of the lower layer film of the novolac.

[Evaluation criteria]
A: Etching rate is less than -10% compared to the novolac lower layer film B: Etching rate is -10% to +5% compared to the novolac lower layer film
C: Etching rate is more than +5% compared to the lower layer of novolak

<Examples 38-39>
Next, each solution of the lower layer film forming material for lithography containing AlOH-XBisN-1 or AlOH-BisF-1 obtained in Examples 1-1 and 2-1 was applied onto a SiO ₂ substrate with a film thickness of 300 nm. A lower layer film having a thickness of 70 nm was formed by coating the film on the substrate and baking it at 240° C. for 60 seconds and then at 400° C. for 120 seconds. An ArF resist solution was applied onto this lower layer film and baked at 130° C. for 60 seconds to form a photoresist layer with a thickness of 140 nm. The ArF resist solution was prepared by blending 5 parts by mass of the compound of the following formula (11), 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 2 parts by mass of tributylamine, and 92 parts by mass of PGMEA. The prepared one was used.

The compound of formula (11) contains 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, and azobisisobutyronitrile. 0.38 g was dissolved in 80 mL of tetrahydrofuran to prepare a reaction solution. This reaction solution was polymerized for 22 hours under a nitrogen atmosphere while maintaining the reaction temperature at 63° C., and then the reaction solution was dropped into 400 mL of n-hexane. The resulting resin thus obtained was coagulated and purified, and the resulting 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, and do not indicate a block copolymer.

Next, the photoresist layer was exposed to light using an electron beam lithography system (manufactured by Elionix Co., Ltd.; ELS-7500, 50 keV), baked at 115°C for 90 seconds (PEB), and 2.38% by mass tetramethylammonium hydroxide ( TMAH) aqueous solution for 60 seconds to obtain a positive resist pattern.

The shapes and defects of the obtained 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.
Regarding the shape of the resist pattern after development, those with no pattern collapse and good rectangularity were evaluated as "good", and the others were evaluated as "poor". Further, as a result of the above observation, the minimum line width with no pattern collapse and good rectangularity was used as an evaluation index as "resolution". Furthermore, the minimum amount of electron beam energy capable of drawing a good pattern shape was defined as "sensitivity" and was used as an evaluation index.
The evaluation results are shown in Table 8.

<Comparative example 2>
A photoresist layer was directly formed on the SiO ₂ substrate to obtain a positive resist pattern in the same manner as in Example 38, except that the lower layer film was not formed. The results are shown in Table 8.

[Comparative example 2]

As is clear from Table 8, in the examples using the lower layer forming material containing the compound of this embodiment, it was confirmed that the resist pattern shape after development was good and no defects were observed. It was confirmed that both resolution and sensitivity were significantly superior to Comparative Example 2 in which the formation of the lower layer film was omitted.
The difference in the shape of the resist pattern after development showed that the lithography underlayer film forming materials used in Examples 38 to 39 had good adhesion to the resist material.

As is clear from Table 1, Examples 1-1 and 2-1 using AlOH-XBisN-1 or AlOH-BisF-1 had better heat resistance, solubility, and etching resistance than Comparative Example 1. At least it was confirmed that it was also good in terms of. On the other hand, in Comparative Example 1 using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resin), the etching resistance was poor.
Further, in Examples 38 to 39, it was confirmed that the resist pattern shape after development was good and no defects were observed. Furthermore, it was also confirmed that both resolution and sensitivity were significantly superior to Comparative Example 2 in which the formation of the lower layer film was omitted.
In addition, it was confirmed from the difference in the shape of the resist pattern after development that the lithography underlayer film forming materials used in Examples 38 to 39 had good adhesion to the resist material.

<Examples 40-41>
A solution of the lower layer film forming material for lithography of Examples 1-1 and 2-1 using AlOH-XBisN-1 or AlOH-BisF-1 was coated on a SiO ₂ substrate with a film thickness of 300 nm, and heated at 240°C for 60 minutes. A lower layer film having a thickness of 80 nm was formed by further baking at 400° C. for 120 seconds. A silicon-containing intermediate layer material was applied onto this lower layer film and baked at 200° C. for 60 seconds to form an intermediate layer film with a thickness of 35 nm. Further, the ArF resist solution described above was applied onto this intermediate layer film and baked at 130° C. for 60 seconds to form a photoresist layer with a thickness of 150 nm. Note that as the silicon-containing intermediate layer material, a silicon-containing polymer obtained below was used.

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 temperature of the solution was raised to 35°C. Then, 5 g of oxalic acid was added dropwise, and the temperature was then raised to 80°C to perform a silanol condensation reaction. Next, 200 g of diethyl ether was added, the aqueous layer was separated, the organic liquid layer was washed twice with ultrapure water, 200 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the liquid was heated to 60°C under reduced pressure. THF and diethyl ether water were removed to obtain a silicon atom-containing polymer.

Next, the photoresist layer was exposed to light using a mask using an electron beam lithography system (manufactured by Elionix Co., Ltd.; ELS-7500, 50 keV), baked at 115°C for 90 seconds (PEB), and 2.38% by mass tetramethylammonium hydroxide was added to the photoresist layer. By developing with a (TMAH) aqueous solution for 60 seconds, a positive resist pattern of 55 nm L/S (1:1) was obtained.

Thereafter, dry etching of the silicon-containing intermediate layer film (SOG) was performed using RIE-10NR manufactured by Samco International Co., Ltd. using the obtained resist pattern as a mask. Dry etching processing of the lower layer film used as a mask and dry etching processing of the SiO ₂ film using the obtained lower layer film pattern as a mask were sequentially performed.

Each etching condition is as shown below.
Etching conditions for resist pattern on resist intermediate layer film
Output: 50W
Pressure: 20Pa
Time: 1min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50:8:2 (sccm)
Etching conditions for the resist lower layer film of the resist intermediate film pattern
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50:5:5 (sccm)
Etching conditions for SiO ₂ film of 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 (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 lower layer film of this embodiment was not used. In the example shown above, the shape of the SiO ₂ film after etching in multilayer resist processing was rectangular, and it was confirmed that the shape was good with no defects observed.

[Examples 42 to 45]
Optical component forming compositions were prepared using the compounds synthesized in the above Synthesis Examples with the formulations shown in Table 9 below. Note that among the components of the optical component forming composition in Table 9, the following were used for the acid generator, crosslinking agent, acid diffusion inhibitor, and solvent.
・Acid generator: Midori Kagaku Co., Ltd. ditertiary butyl diphenyliodonium nonafluoromethanesulfonate (DTDPI)
・Crosslinking agent: Nikalac MX270 (Nicalac) manufactured by Sanwa Chemical Co., Ltd.
Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)
A uniform optical component forming composition was spin-coated onto a clean silicon wafer, and then prebaked (PB) in an oven at 110° C. to form an optical component forming film with a thickness of 1 μm. The prepared optical component forming composition was evaluated as "A" if the film formed well, and "C" if the formed film had defects.

A uniform optical component forming composition was spin-coated onto a clean silicon wafer, and then subjected to PB in an oven at 110° C. to form a film with a thickness of 1 μm. The refractive index (λ=589.3 nm) of the film at 25° C. was measured using a multi-incident angle spectroscopic ellipsometer VASE manufactured by JA Woollam. The prepared film was evaluated as "A" if the refractive index was 1.65 or more, "B" if it was 1.6 or more and less than 1.65, and "C" if it was less than 1.6. . Moreover, when the transparency (λ=632.8 nm) was 90% or more, it was evaluated as "A", and when it was less than 90%, it was evaluated as "C".

[Examples 46 to 49]
Using the compounds synthesized in the above Synthesis Examples and Synthesis Examples, resist compositions were prepared according to the formulations shown in Table 10 below. Note that among the components of the resist composition in Table 10, the following were used for the radical generator, radical diffusion inhibitor, and solvent.
・Radical polymerization initiator: IRGACURE184 manufactured by BASF
・Radical diffusion control agent: IRGACURE1010 manufactured by BASF
Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)

[Evaluation method]
(1) Storage stability of resist composition and thin film formation The storage stability of resist composition is determined by leaving it at 23°C and 50% RH for 3 days after creating the resist composition, and visually checking for the presence or absence of precipitation. Evaluation was made by observation. The resist composition after standing for 3 days was evaluated as A if it was a homogeneous solution and had no precipitation, and was evaluated as C if there was precipitation. Further, a uniform resist composition was spin-coated onto a clean silicon wafer, and then pre-exposure baking (PB) was performed in an oven at 110° C. to form a resist film with a thickness of 40 nm. The prepared resist composition was evaluated as A when the thin film was formed well, and C when the formed film had defects.

(2) Pattern evaluation of resist pattern A uniform resist composition was spin-coated onto a clean silicon wafer, and then pre-exposure baking (PB) was performed in an oven at 110° C. to form a resist film with a thickness of 60 nm. The obtained resist film was irradiated with an electron beam using an electron beam drawing device (ELS-7500, manufactured by Elionix Co., Ltd.) with a line and space setting of 1:1 at intervals of 50 nm, 40 nm, and 30 nm. . After the irradiation, each resist film was heated at a predetermined temperature for 90 seconds, and developed by immersing it in PGME for 60 seconds. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern. The lines and spaces of the formed resist pattern were observed using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), and the reactivity of the resist composition to electron beam irradiation was evaluated.
Sensitivity was expressed as the minimum amount of energy per unit area required to obtain a pattern, and was evaluated according to the following.
A: When a pattern is obtained at less than 50 μC/cm2 C: When a pattern is obtained at 50 μC/cm2 or more For pattern formation, observe the obtained pattern shape with a SEM (Scanning Electron Microscope). and evaluated according to the following.
A: When a rectangular pattern is obtained B: When a nearly rectangular pattern is obtained C: When a non-rectangular pattern is obtained

As described above, the present invention is not limited to the embodiments and examples described above, and changes can be made as appropriate without departing from the gist thereof.

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 provides a good resist pattern shape.

In addition, a wet process is applicable, and compounds, resins, and film-forming compositions for lithography useful for forming a photoresist underlayer film with excellent heat resistance and etching resistance can be realized. Since this film-forming composition for lithography uses a compound or resin with a specific structure that has high heat resistance and high solvent solubility, deterioration of the film during high-temperature baking is suppressed, and oxygen plasma etching, etc. It is possible to form a resist and an underlying film that also have excellent etching resistance. Furthermore, when a lower layer film is formed, it has excellent adhesion with the resist layer, so that an excellent resist pattern can be formed.

Furthermore, since it has a high refractive index and coloration is suppressed by low-temperature to high-temperature treatment, it is useful as a composition for forming various optical components.

Therefore, the present invention is applicable to, for example, electrical insulating materials, resist resins, semiconductor sealing resins, printed wiring board adhesives, electrical laminates mounted on electrical equipment, electronic equipment, industrial equipment, etc.・Prepreg matrix resins used in electronic equipment, industrial equipment, etc., build-up laminate materials, resins for fiber-reinforced plastics, sealing resins for liquid crystal display panels, paints, various coating agents, adhesives, coatings for semiconductors In addition to being used in the form of adhesives, resins for resists for semiconductors, resins for forming lower layer films, films and sheets, plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast improvement lenses, etc.) Can be widely and effectively used in optical components such as retardation films, electromagnetic shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulation films for multilayer printed wiring boards, and photosensitive optical waveguides. It is.

This application is based on a Japanese patent application (Japanese Patent Application No. 2016-178433) filed with the Japan Patent Office on September 13, 2016, the contents of which are incorporated herein by reference.

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

Claims (25)

A compound represented by the following formula (0) or the following formula (1 -1 ).

(0)
(In formula (0), R ^Y is a hydrogen atom,
R ^Z is an alicyclic hydrocarbon group, a double bond, an N-valent hydrocarbon group having 1 to 60 carbon atoms, which may have a heteroatom or an aromatic group, or a single bond;
R ^T each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an optionally substituted alkenyl group with 2 to 30 carbon atoms, an optionally substituted alkoxy group with 1 to 30 carbon atoms, 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 group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond ,
X indicates an oxygen atom,
m is each independently an integer from 0 to 9 ,
N is an integer from 1 to 4, where N is an integer of 2 or more, the N structural formulas in [ ] may be the same or different,
Each r is independently an integer of 0 to 2.
Here, at least one of R ^T in formula (0) exists as a hydroxyl group, and in each of the two aryl structures shown in formula (0), at least one of R ^T has 2 to 2 carbon atoms. It exists as 30 alkenyl groups. )

(1 -1 )
(In formula ( 1-1 ), R ⁰ has the same meaning as R ^Y above,
R ¹ is an alicyclic hydrocarbon group, a double bond, an n-valent hydrocarbon group having 1 to 60 carbon atoms, which may have a heteroatom or an aromatic group, or a single bond;
R ⁴ to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. 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, a carboxylic acid group, a thiol group, or is a hydroxyl group, and the alkyl group, aryl group, alkenyl group, and alkoxy group may contain an ether bond, a ketone bond, or an ester bond;
R ⁶ to R ⁷ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. an alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol group, which may have
R ¹⁰ to R ¹¹ are each independently a hydrogen atom ,
m ⁴ and m ⁵ are each independently an integer of 0 to 9, m ⁶ and m ⁷ are each independently an integer of 0 to 7,
n has the same meaning as N above, where n is an integer of 2 or more, the n structural formulas in [ ] may be the same or different,
p ² to p ⁵ each independently have the same meaning as r.
Here, at least one of R ⁶ to R ⁷ in formula (1-1) exists as an alkenyl group having 2 to 30 carbon atoms. ) 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 has the same meaning as the above R ^Y ,
R ^1A is an alicyclic hydrocarbon group, a double bond, an n ^A valent hydrocarbon group having 1 to 30 carbon atoms, which may have a heteroatom or an aromatic group, or a single bond;
R ^2A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an optionally substituted alkenyl group with 2 to 30 carbon atoms, an optionally substituted alkoxy group with 1 to 30 carbon atoms, 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 group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond ,
^nA has the same meaning as N above, where ^nA is an integer of 2 or more, the structural formulas in [ ] of ^nA may be the same or different,
X ^A indicates an oxygen atom,
m ^2A are each independently an integer from 0 to 7 ,
q ^A is each independently 0 or 1.
Here, at least one of R ^2A in formula (2) exists as a hydroxyl group, and in each of the two aryl structures shown in formula (2), at least one of R ^2A has 2 to 2 carbon atoms. It exists as 30 alkenyl groups. ) The compound according to claim 1 , 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 meanings as R ⁶ to R ⁷ above,
R ¹² to R ¹³ have the same meanings as R ¹⁰ to R ¹¹ above,
m ⁸ and m ⁹ are each independently an integer of 0 to 8.
Here, at least one of R ⁶ to R ⁷ in formula (1-2) exists as an alkenyl group having 2 to 30 carbon atoms. ) The compound according to claim 2, 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 have the same meanings as above,
R ^3A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an alkenyl group, a halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol group having 2 to 30 carbon atoms , which may be
R ^4A is each independently a hydrogen atom,
m ^6A are each independently an integer of 0 to 5.
Here, in each of the two aryl structures shown in formula (2-1), at least one of R ^3A exists as an alkenyl group having 2 to 30 carbon atoms. ) A resin having a structure represented by the following formula (3).

(3)
(In formula (3), L is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may have a substituent, or a linear, branched or cyclic alkylene group having 6 to 30 carbon atoms which may have a substituent. 30 arylene groups, an alkoxylene group having 1 to 30 carbon atoms which may have a substituent, or a single bond, and the alkylene group, the arylene group, and the alkoxylene group are an ether bond, a ketone bond, or an ester bond. may include a bond,
R ⁰ is a hydrogen atom ,
R ¹ is an alicyclic hydrocarbon group, a double bond, an n-valent hydrocarbon group having 1 to 60 carbon atoms, which may have a heteroatom or an aromatic group, or a single bond;
R ² to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. 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, a carboxylic acid group, a thiol group, or is a hydroxyl group, and the alkyl group, aryl group, alkenyl group, and alkoxy group may contain an ether bond, a ketone bond, or an ester bond;
m ² and m ³ are each independently an integer of 0 to 8,
m ⁴ and m ⁵ are each independently an integer from 0 to 9 ,
n is an integer from 1 to 4, where n is an integer of 2 or more, the n structural formulas in [ ] may be the same or different, and p ² to p ⁵ are: Each independently is an integer from 0 to 2.
Here, at least one of R ² to R ⁵ in formula (3) exists as a hydroxyl group, and at least one of R ² to R ⁵ exists as an alkenyl group having 2 to 30 carbon atoms. ) A resin 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 is a hydrogen atom ,
R ^1A is an alicyclic hydrocarbon group, a double bond, an n ^A valent hydrocarbon group having 1 to 30 carbon atoms, which may have a heteroatom or an aromatic group, or a single bond;
R ^2A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent; an optionally substituted alkenyl group with 2 to 30 carbon atoms, an optionally substituted alkoxy group with 1 to 30 carbon atoms, 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 group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond ,
n ^A is an integer from 1 to 4, where n ^A is an integer of 2 or more, the n ^A structural formulas in [ ] may be the same or different,
X ^A indicates an oxygen atom,
m ^2A are each independently an integer from 0 to 7 ,
q ^A is each independently 0 or 1.
Here, at least one of R ^2A in formula (4) exists as a hydroxyl group, and in each of the two aryl structures shown in formula (4), at least one of R ^2A has 2 to 2 carbon atoms. It exists as 30 alkenyl groups. ) A composition containing one or more selected from the group consisting of the compound according to any one of claims 1 to 4 and the resin according to claim 5 or 6 . 8. The composition according to claim 7 , further comprising a solvent. The composition according to claim 7 or 8 , further comprising an acid generator. Composition according to any one of claims 7 to 9 , further comprising a crosslinking agent. The crosslinking agent is at least one selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amino compound, a benzoxazine compound, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an isocyanate compound, and an azide compound. 11. The composition of claim 10 . 12. The composition according to claim 10 or 11 , wherein the crosslinking agent has at least one allyl group. The composition according to any one of claims 10 to 12 , wherein the content of the crosslinking agent is 0.1 to 50% by weight based on the total weight of the solid component. The composition according to any one of claims 10 to 13 , further comprising a crosslinking promoter. The composition according to claim 14 , wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids. The composition according to claim 14 or 15 , wherein the content of the crosslinking accelerator is 0.1 to 5% by weight based on the total weight of the solid component. The composition according to any one of claims 7 to 16 , further comprising a radical polymerization initiator. The composition according to claim 17 , wherein the radical polymerization initiator is at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator. The composition according to claim 18 , wherein the content of the radical polymerization initiator is 0.05 to 25% by weight based on the total weight of the solid component. The composition according to any one of claims 8 to 19 , which is used for forming a film for lithography. The composition according to any one of claims 8 to 19 , which is used for forming a resist permanent film. The composition according to any one of claims 8 to 19 , which is used for forming an optical component. A method for forming a resist pattern, comprising the steps of forming a photoresist layer on a substrate using the composition according to claim 20 , and then irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer. After forming an underlayer film on a substrate using the composition according to claim 20 and forming at least one photoresist layer on the underlayer film, radiation is applied to a predetermined region of the photoresist layer. A resist pattern forming method including the steps of irradiating and developing. A lower layer film is formed on the substrate using the composition according to claim 20 , an intermediate layer film is formed on the lower layer film using a resist intermediate layer film material, and at least After forming one photoresist layer, a predetermined region of the photoresist layer is irradiated with radiation and developed to form a resist pattern, and then the intermediate layer film is etched using the resist pattern as a mask, A circuit pattern forming method comprising the steps of etching the lower layer film using the obtained intermediate layer film pattern as an etching mask, and etching the substrate using the obtained lower layer film pattern as an etching mask to form a pattern on the substrate.