JP7090843B2 - Compounds, resins, compositions, pattern forming methods and purification methods - Google Patents

Description

The present invention relates to a compound having a specific structure, a resin, a composition containing these, a pattern forming method using the composition, and a method for purifying a substance.

In the manufacture of semiconductor devices, microfabrication by lithography using a photoresist material is performed, but in recent years, with the increase in integration and speed of LSI, further miniaturization by pattern rules is required. In lithography using light exposure, which is currently used as a general-purpose technology, the limit of essential resolution derived from the wavelength of a light source is approaching.

The light source for lithography used in forming the resist pattern has a shorter wavelength from a KrF excimer laser (248 nm) to an ArF excimer laser (193 nm). However, as the resist pattern becomes finer, there arises a problem of resolution or a problem that the resist pattern collapses after development, so that it is desired to reduce the thickness of the resist. In response to such a demand, it is difficult to obtain a resist pattern film thickness sufficient for substrate processing simply by thinning the resist. Therefore, not only the resist pattern but also a process of creating a resist underlayer film between the resist and the semiconductor substrate to be processed and giving the resist underlayer film a function as a mask at the time of substrate processing is required.

Currently, various resist underlayer films for such processes are known. For example, a resist underlayer film for lithography having a selection ratio of a dry etching rate close to that of a resist, unlike a conventional resist underlayer film having a high etching rate, can be mentioned. As a material for forming such a resist underlayer film for lithography, it contains a resin component having at least a substituent having at least a substituent that desorbs a terminal group to form a sulfonic acid residue when a predetermined energy is applied, and a solvent. A lower layer film forming material for a multilayer resist process has been proposed (see, for example, Patent Document 1). Further, a resist underlayer film for lithography having a selection ratio of a dry etching rate smaller than that of a resist can also be mentioned. As a material for forming such a resist underlayer film for lithography, a resist underlayer film material containing a polymer having a specific repeating unit has been proposed (see, for example, Patent Document 2). Further, a resist underlayer film for lithography having a selection ratio of a dry etching rate smaller than that of a semiconductor substrate can be mentioned. As a material for forming such a resist underlayer film for lithography, a resist underlayer film material containing a polymer obtained by copolymerizing a repeating unit of acenaphthylene and a repeating unit having a substituted or unsubstituted hydroxy group is used. It has been proposed (see, for example, Patent Document 3).

On the other hand, as a material having high etching resistance in this type of resist underlayer film, a chemical vapor deposition thin film deposition method (Chemical Vapor Deposition, hereinafter also referred to as “CVD”) using methane gas, ethane gas, acetylene gas or the like as raw materials is used. The formed amorphous carbon underlayer film is well known. However, from the viewpoint of the process, there is a demand for a resist underlayer film material capable of forming a resist underlayer film by a wet process such as a spin coating method or screen printing.

Recently, there has been a demand for forming a resist underlayer film for lithography for a layer to be processed having a complicated shape, and there is a demand for a resist underlayer film material capable of forming an underlayer film having excellent embedding property and film surface flattening property. There is.

Regarding the method for forming the intermediate layer used in the formation of the resist underlayer film in the three-layer process, for example, a method for forming a silicon nitride film (see, for example, Patent Document 4) and a method for forming a CVD for a silicon nitride film (for example, see Patent Document 4). , Patent Document 5) is known. Further, as an intermediate layer material for a three-layer process, a material containing a silicon compound based on silsesquioxane is known (see, for example, Patent Documents 6 and 7).

The present inventors have proposed an underlayer film forming composition for lithography containing a specific compound or resin (see, for example, Patent Document 8).

Various optical component forming compositions have been proposed, such as acrylic resins (see, for example, Patent Documents 9 to 10) and polyphenols having a specific structure derived from an allyl group (for example, patents). Reference 11) has been proposed.

Japanese Unexamined Patent Publication No. 2004-177668 Japanese Unexamined Patent Publication No. 2004-271883 Japanese Unexamined Patent Publication No. 2005-250434 JP-A-2002-334869 International Publication No. 2004/06637 Japanese Unexamined Patent Publication No. 2007-226170 Japanese Unexamined Patent Publication No. 2007-226204 International Publication No. 2013/024779 Japanese Unexamined Patent Publication No. 2010-138393 JP-A-2015-174877 International Publication No. 2014/123005

As described above, many underlayer film forming materials for lithography have been proposed in the past, but they have high levels of high solvent solubility, heat resistance and etching resistance to which wet processes such as spin coating and screen printing can be applied. There is nothing to do, and the development of new materials is required.

Further, although many compositions for optical members have been proposed in the past, none of them have both heat resistance, transparency and refractive index at a high level, and development of a new material is required.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a compound, a resin and a composition which are excellent in solvent solubility, can be applied to a wet process, and are useful for forming a film for lithography having excellent heat resistance and etching resistance. Another object of the present invention is to provide a pattern forming method using the composition.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by using a compound having a specific structure, and have completed the present invention.

（式（Ａ）中、Ｒ^Ｙは、水素原子、炭素数１～３０の直鎖状、分岐状若しくは環状のアルキル基又は炭素数６～３０のアリール基であり、
Ｒ^Ｚは、置換基を有していてもよい炭素数６～３０のアリール基を含む炭素数６～６０のｍ価の基であって、該アリール基は置換基を有していてもよい炭素数１～３０の直鎖状若しくは分岐状のアルキル基又は水酸基を有し、該アリール基は、水酸基を有する場合、ヨウ素原子及び／又はメトキシ基を有さず、
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の直鎖状、分岐状若しくは環状のアルキル基、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、カルボキシル基 、チオール基、水酸基の水素原子が酸解離性基で置換された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、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、ｎは、各々独立して、０～８の整数であり、ここで、ｎの少なくとも１つは１～８の整数であり、ｍは、１～４の整数であり、ｋは、各々独立して、０～２の整数である。）
［２］前記式（Ａ）で表される化合物が、下記式（１）で表される化合物である、前記［１］に記載の化合物。

（式（１）中、Ｒ^Ｙ、Ｒ^Ｚ、ｍ及びｋは、上記式（Ａ）で説明したものと同義である。
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の直鎖状、分岐状若しくは環状のアルキル基、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、カルボキシル基 又はチオール基であり、
Ｒ^４Ａは、各々独立して、水素原子又は酸解離性基であり、ここで、Ｒ^４Ａの少なくとも１つは水素原子であり、
ｍ^６Ａは、各々独立して、０～７の整数である。）
［３］前記式（１）で表される化合物が、下記式（１’）で表される化合物である、前記［２］に記載の化合物。

（式（１’）中、Ｒ^Ｚは、前記式（Ａ）で説明したものと同義である。）
［４］前記式（１’）で表される化合物が、下記式（２）で表される化合物である、前記［３］に記載の化合物。

（式（２）中、Ｒ^３Ｂは、各々独立して、置換基を有していてもよい炭素数１～３０の直鎖状若しくは分岐状のアルキル基又は水酸基であり、ｍ^６Ｂは、１～５の整数である。）
［５］前記式（２）で表される化合物が、下記式（２－１）～式（２－１２）で表される群から選ばれる化合物である、前記［４］に記載の化合物。

［６］前記［１］～［５］のいずれかに記載の化合物に由来する構成単位を有する、樹脂。
［７］前記［１］～［５］のいずれかに記載の化合物及び前記［６］に記載の樹脂からなる群より選ばれる１種類以上を含有する、組成物。
［８］前記［１］～［５］のいずれかに記載の化合物及び前記［６］に記載の樹脂からなる群より選ばれる１種類以上を含有する、光学部品形成用組成物。
［９］前記［１］～［５］のいずれかに記載の化合物及び前記［６］に記載の樹脂からなる群より選ばれる１種類以上を含有する、リソグラフィー用膜形成組成物。
［１０］前記［１］～［５］のいずれかに記載の化合物及び前記［６］に記載の樹脂からなる群より選ばれる１種類以上を含有する、レジスト組成物。
［１１］溶媒をさらに含有する、前記［１０］に記載のレジスト組成物。
［１２］酸発生剤をさらに含有する、前記［１０］又は［１１］に記載のレジスト組成物。
［１３］酸拡散制御剤をさらに含有する、前記［１０］～［１２］のいずれかに記載のレジスト組成物。
［１４］前記［１０］～［１３］のいずれかに記載のレジスト組成物を用いて、基板上にレジスト膜を形成する工程と、
形成された前記レジスト膜の少なくとも一部を露光する工程と、
露光した前記レジスト膜を現像してレジストパターンを形成する工程と、を含む、レジストパターン形成方法。
［１５］前記［１］～［５］のいずれかに記載の化合物及び前記［６］に記載の樹脂からなる群より選ばれる１種類以上である成分（Ａ）と、 ジアゾナフトキノン光活性化合物（Ｂ）と、 溶媒と、を含有する感放射線性組成物であって、 前記溶媒の含有量が、前記感放射線性組成物の総量１００質量％に対して２０～９９質量％であり、 前記溶媒以外の成分の含有量が、前記感放射線性組成物の総量１００質量％に対して１～８０質量％である、感放射線性組成物。
［１６］前記成分（Ａ）と、前記ジアゾナフトキノン光活性化合物（Ｂ）と、前記感放射線性組成物に任意に含まれ得るその他の任意成分（Ｄ）と、の含有量比（（Ａ）／（Ｂ）／（Ｄ））が、前記感放射線性組成物の固形分１００質量％に対して、１～９９質量％／９９～１質量％／０～９８質量％である、前記［１５］に記載の感放射線性組成物。
［１７］スピンコートによりアモルファス膜を形成することができる、前記［１５］又は［１６］に記載の感放射線性組成物。
［１８］前記［１５］～［１７］のいずれかに記載の感放射線性組成物を用いて、基板上にアモルファス膜を形成する工程を含む、アモルファス膜の製造方法。
［１９］前記［１５］～［１７］のいずれかに記載の感放射線性組成物を用いて、基板上にレジスト膜を形成する工程と、 形成された前記レジスト膜の少なくとも一部を露光する工程と、露光した前記レジスト膜を現像して、レジストパターンを形成する工程を含む、レジストパターン形成方法。
［２０］前記［１］～［５］のいずれかに記載の化合物及び前記［６］に記載の樹脂からなる群より選ばれる種類以上を含有する、リソグラフィー用下層膜形成材料。
［２１］前記［２０］に記載のリソグラフィー用下層膜形成材料と、溶媒と、を含有する、リソグラフィー用下層膜形成用組成物。
［２２］酸発生剤をさらに含有する、前記［２１］に記載のリソグラフィー用下層膜形成用組成物。
［２３］架橋剤をさらに含有する、前記［２１］又は［２２］に記載のリソグラフィー用下層膜形成用組成物。
［２４］前記［２１］～［２３］のいずれかに記載のリソグラフィー用下層膜形成用組成物を用いて、基板上に下層膜を形成する工程を含む、リソグラフィー用下層膜の製造方法。
［２５］前記［２１］～［２３］のいずれかに記載のリソグラフィー用下層膜形成用組成物を用いて、基板上に、下層膜を形成する工程と、
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する工程と、
前記フォトレジスト層の所定の領域に放射線を照射し、現像してレジストパターンを形成する工程と、を有する、レジストパターン形成方法。
［２６］前記［２１］～［２３］のいずれかに記載のリソグラフィー用下層膜形成用組成物を用いて、基板上に下層膜を形成する工程と、
前記下層膜上に、珪素原子を含有するレジスト中間層膜材料を用いて中間層膜を形成する工程と、
前記中間層膜上に、少なくとも１層のフォトレジスト層を形成する工程と、
前記フォトレジスト層の所定の領域に放射線を照射し、現像してレジストパターンを形成する工程と、
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て、中間層膜パターンを形成する工程と、
前記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て、下層膜パターンを形成する工程と、
前記下層膜パターンをエッチングマスクとして前記基板をエッチングして、前記基板にパターンを形成する工程と、を有する、回路パターン形成方法。
［２７］前記［１］～［５］のいずれかに記載の化合物及び前記［６］に記載の樹脂からなる群より選ばれる１種類以上を、溶媒に溶解させて溶液（Ｓ）を得る工程と、 得られた溶液（Ｓ）と酸性の水溶液とを接触させて、前記化合物及び／又は前記樹脂中の不純物を抽出する第一抽出工程とを含み、前記溶液（Ｓ）を得る工程で用いる溶媒が、水と混和しない溶媒を含む、精製方法。
［２８］前記酸性の水溶液が、鉱酸水溶液又は有機酸水溶液であり、 前記鉱酸水溶液が、塩酸、硫酸、硝酸及びリン酸からなる群より選ばれる１種以上を水に溶解させた鉱酸水溶液であり、 前記有機酸水溶液が、酢酸、プロピオン酸、蓚酸、マロン酸、コハク酸、フマル酸、マレイン酸、酒石酸、クエン酸、メタンスルホン酸、フェノールスルホン酸、ｐ－トルエンスルホン酸及びトリフルオロ酢酸からなる群より選ばれる１種以上を水に溶解させた有機酸水溶液である、前記［２７］に記載の精製方法。
［２９］前記水と混和しない溶媒が、トルエン、２－ヘプタノン、シクロヘキサノン、シクロペンタノン、メチルイソブチルケトン、プロピレングリコールモノメチルエーテルアセテート及び酢酸エチルからなる群より選ばれる１種以上の溶媒である、前記［２７］又は［２８］に記載の精製方法。
［３０］前記第一抽出工程後、前記化合物及び／又は前記樹脂を含む溶液相を、さらに水に接触させて、前記化合物及び／又は前記樹脂中の不純物を抽出する第二抽出工程含む、前記［２７］～［２９］のいずれかに記載の精製方法。That is, the present invention is as follows.
[1] A compound represented by the following formula (A).

(In the formula (A), ^RY is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
R ^Z is a m-valent group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and the aryl group may have a substituent. It has a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms, and when the aryl group has a hydroxyl group, it does not have an iodine atom and / or a methoxy group.
Each ^RT has a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have a substituent and has 6 to 30 carbon atoms. Aryl group, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, and a carboxyl group. A group or hydroxyl group in which a hydrogen atom of a group, a thiol group or a hydroxyl group is substituted with an acid dissociable group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group have an ether bond, a ketone bond or an ester bond. May include, where at least one of ^RTs is a hydroxyl group, n is independently an integer of 0-8, where at least one of n is an integer of 1-8. M is an integer of 1 to 4, and k is an independently of an integer of 0 to 2. )
[2] The compound according to the above [1], wherein the compound represented by the formula (A) is a compound represented by the following formula (1).

(In the formula (1), ^RY , ^RZ , m and k are synonymous with those described in the above formula (A).
Each of R ^3A independently has a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. Aryl group, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group or a thiol group.
Each R ^4A is independently a hydrogen atom or an acid dissociating group, where at least one of the R ^4A is a hydrogen atom.
m ^6A is an integer of 0 to 7 independently of each other. )
[3] The compound according to the above [2], wherein the compound represented by the formula (1) is a compound represented by the following formula (1').

(In the formula (1'), ^RZ is synonymous with the one described in the above formula (A).)
[4] The compound according to the above [3], wherein the compound represented by the formula (1') is a compound represented by the following formula (2).

In the formula (2), R ^3B is a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms which may independently have a substituent, and m ^6B is 1 It is an integer of ~ 5.)
[5] The compound according to the above [4], wherein the compound represented by the formula (2) is a compound selected from the group represented by the following formulas (2-1) to (2-12).

[6] A resin having a structural unit derived from the compound according to any one of the above [1] to [5].
[7] A composition containing at least one selected from the group consisting of the compound according to any one of the above [1] to [5] and the resin according to the above [6].
[8] An optical component forming composition containing at least one selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6].
[9] A film forming composition for lithography containing at least one selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6].
[10] A resist composition containing at least one selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6].
[11] The resist composition according to the above [10], further containing a solvent.
[12] The resist composition according to the above [10] or [11], further containing an acid generator.
[13] The resist composition according to any one of [10] to [12] above, further containing an acid diffusion control agent.
[14] A step of forming a resist film on a substrate using the resist composition according to any one of [10] to [13] above, and
A step of exposing at least a part of the formed resist film, and
A resist pattern forming method comprising a step of developing the exposed resist film to form a resist pattern.
[15] A component (A) that is one or more selected from the group consisting of the compound according to any one of the above [1] to [5] and the resin according to the above [6], and a diazonaphthoquinone photoactive compound ( A radiation-sensitive composition containing B) and a solvent, wherein the content of the solvent is 20 to 99% by mass with respect to 100% by mass of the total amount of the radiation-sensitive composition, and the solvent. A radiation-sensitive composition, wherein the content of the components other than the above is 1 to 80% by mass with respect to 100% by mass of the total amount of the radiation-sensitive composition.
[16] The content ratio ((A)) of the component (A), the diazonaphthoquinone photoactive compound (B), and another optional component (D) that can be optionally contained in the radiation-sensitive composition. / (B) / (D)) is 1 to 99% by mass / 99 to 1% by mass / 0 to 98% by mass with respect to 100% by mass of the solid content of the radiation-sensitive composition. ] The radiation-sensitive composition according to.
[17] The radiation-sensitive composition according to the above [15] or [16], wherein an amorphous film can be formed by spin coating.
[18] A method for producing an amorphous film, which comprises a step of forming an amorphous film on a substrate by using the radiation-sensitive composition according to any one of [15] to [17].
[19] Using the radiation-sensitive composition according to any one of the above [15] to [17], a step of forming a resist film on a substrate and exposing at least a part of the formed resist film. A resist pattern forming method comprising a step and a step of developing the exposed resist film to form a resist pattern.
[20] A lower layer film forming material for lithography containing a kind or more selected from the group consisting of the compound according to any one of the above [1] to [5] and the resin according to the above [6].
[21] A composition for forming an underlayer film for lithography, which comprises the material for forming an underlayer film for lithography according to the above [20] and a solvent.
[22] The composition for forming an underlayer film for lithography according to the above [21], which further contains an acid generator.
[23] The composition for forming an underlayer film for lithography according to the above [21] or [22], which further contains a cross-linking agent.
[24] A method for producing an underlayer film for lithography, which comprises a step of forming an underlayer film on a substrate by using the composition for forming an underlayer film for lithography according to any one of the above [21] to [23].
[25] A step of forming a lower layer film on a substrate by using the composition for forming a lower layer film for lithography according to any one of the above [21] to [23].
A step of forming at least one photoresist layer on the underlayer film, and
A resist pattern forming method comprising a step of irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist pattern to form a resist pattern.
[26] A step of forming a lower layer film on a substrate by using the composition for forming a lower layer film for lithography according to any one of the above [21] to [23].
A step of forming an intermediate layer film on the lower layer film using a resist intermediate layer film material containing a silicon atom, and a step of forming the intermediate layer film.
A step of forming at least one photoresist layer on the intermediate layer film and
A step of irradiating a predetermined area of the photoresist layer with radiation and developing the resist layer to form a resist pattern.
A step of etching the intermediate layer film using the resist pattern as a mask to form an intermediate layer film pattern,
A step of etching the lower layer film using the intermediate layer film pattern as an etching mask to form a lower layer film pattern, and a step of forming the lower layer film pattern.
A circuit pattern forming method comprising a step of etching a substrate using the underlayer film pattern as an etching mask to form a pattern on the substrate.
[27] A step of dissolving one or more selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6] in a solvent to obtain a solution (S). And / or a first extraction step of bringing the obtained solution (S) into contact with an acidic aqueous solution to extract impurities in the compound and / or the resin, and the solution (S) is used in the step of obtaining the solution (S). A purification method comprising a solvent in which the solvent is immiscible with water.
[28] The acidic aqueous solution is a mineral acid aqueous solution or an organic acid aqueous solution, and the mineral acid aqueous solution is a mineral acid in which one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitrate and phosphoric acid is dissolved in water. It is an aqueous solution, and the organic acid aqueous solution is acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoro. The purification method according to the above [27], which is an organic acid aqueous solution in which one or more selected from the group consisting of acetic acid is dissolved in water.
[29] The solvent immiscible with water is one or more solvents selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate. The purification method according to [27] or [28].
[30] The present invention comprises a second extraction step after the first extraction step, wherein the solution phase containing the compound and / or the resin is further brought into contact with water to extract impurities in the compound and / or the resin. The purification method according to any one of [27] to [29].

According to the present invention, it is possible to provide a compound, a resin and a composition which are excellent in solvent solubility, can be applied to a wet process, and are useful for forming a film for lithography having excellent heat resistance and etching resistance.

Hereinafter, embodiments of the present invention (hereinafter, also simply referred to as “the present embodiment”) will be described. It should be noted that the following embodiments are examples for explaining the present invention, and the present invention is not limited to the embodiments thereof.

（式（Ａ）中、Ｒ^Ｙは、水素原子、炭素数１～３０の直鎖状、分岐状若しくは環状のアルキル基又は炭素数６～３０のアリール基であり、
Ｒ^Ｚは、置換基を有していてもよい炭素数６～３０のアリール基を含む炭素数６～６０のｍ価の基であって、該アリール基は置換基を有していてもよい炭素数１～３０の直鎖状若しくは分岐状のアルキル基又は水酸基を有し、該アリール基は、水酸基を有する場合、ヨウ素原子及び／又はメトキシ基を有さず、
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の直鎖状、分岐状若しくは環状のアルキル基、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、カルボキシル基 、チオール基、水酸基の水素原子が酸解離性基で置換された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、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、
ｎは、各々独立して０～８の整数であり、ここで、ｎの少なくとも１つは１～８の整数であり、
ｍは、１～４の整数であり、
ｋは、各々独立して０～２の整数である。）[Compound represented by the formula (A)]
The compound of this embodiment is a compound represented by the following formula (A).

(In the formula (A), ^RY is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
R ^Z is a m-valent group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and the aryl group may have a substituent. It has a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms, and when the aryl group has a hydroxyl group, it does not have an iodine atom and / or a methoxy group.
Each ^RT has a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have a substituent and has 6 to 30 carbon atoms. Aryl group, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, and a carboxyl group. A group or hydroxyl group in which a hydrogen atom of a group, a thiol group or a hydroxyl group is substituted with an acid dissociable group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group have an ether bond, a ketone bond or an ester bond. May include,
Here, at least one of ^RT is a hydroxyl group,
n is an integer of 0 to 8 independently, where at least one of n is an integer of 1 to 8.
m is an integer from 1 to 4 and
k is an integer of 0 to 2 independently. )

RZ in the above formula (A) is a m- ^valent group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and the aryl group has a substituent. It has a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms which may be possessed, and the aryl group does not have an iodine atom and / or a methoxy group when it has a hydroxyl group.
The m-valent group is an alkyl group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and a group having 6 to 30 carbon atoms which may have a substituent. It has an alkylene group having 6 to 60 carbon atoms including an aryl group, an alcantryl group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent. One of an alkanetetrayl group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms and 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent. A valent aromatic group, a divalent aromatic group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms may have a substituent, and a divalent aromatic group having 6 to 60 carbon atoms may have a substituent. A trivalent aromatic group having 6 to 60 carbon atoms including an aryl group of to 30 and a tetravalent aromatic group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent. Represents a group. Here, the aryl group has a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms which may have a substituent, and the aryl group has an iodine atom and a hydroxyl group when it has a hydroxyl group. / Or does not have a methoxy group. Further, the m-valent group may have a double bond, a heteroatom young or an aromatic group having 6 to 30 carbon atoms.
Since the R ^Z in the above formula (A) has a specific structure as described above, the compound of the present embodiment has high heat resistance, can impart a good resist pattern shape, and is also excellent in etching resistance. ..

From the viewpoint of flatness, the m-valent group may have an alkyl group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent and a substituent. A monovalent aromatic group having 6 to 60 carbon atoms including a good aryl group having 6 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms which may have a substituent. It is preferably a divalent aromatic group having 6 to 60 carbon atoms and containing an aryl group having 6 to 30 carbon atoms which may have a group or a substituent.
Further, from the viewpoint of thermal stability, an alkyl group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent and an alkyl group having 6 to 60 carbon atoms which may have a substituent may be used. An alkylene group having 6 to 60 carbon atoms including 30 aryl groups, a monovalent aromatic group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent. It is preferably a divalent aromatic group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may be possessed.

It is a monovalent group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and the aryl group may have a substituent having 1 to 1 carbon atoms. Those having 30 linear or branched alkyl groups or hydroxyl groups are not particularly limited, but for example, methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, and the like. Examples thereof include pentaphenyl group, butylmethylphenyl group, hydroxyphenyl group, dihydroxyphenyl group, fluoromethylphenyl group and the like.
Here, the branched alkyl group is not particularly limited, and for example, in the case of a butyl group, an n-butyl group, a t-butyl group, an i-butyl group, an s-butyl group and the like are included.

It is a divalent group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and the aryl group may have a substituent and has 1 to 1 carbon atoms. The group having 30 linear or branched alkyl groups or hydroxyl groups is not particularly limited, but for example, a methylphenylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylphenylene group, a propylphenylene group, a butylphenylene group, and the like. Examples thereof include a pentaphenylene group, a butylmethylphenylene group, a hydroxyphenylene group, a dihydroxyphenylene group, a fluoromethylphenylene group and the like.

It is a trivalent group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and the aryl group may have a substituent having 1 to 1 carbon atoms. Those having 30 linear or branched alkyl groups or hydroxyl groups are not particularly limited, but for example, methylbenzenetriyl group, dimethylbenzenetriyl group, trimethylbenzenetriyl group, ethylbenzenetriyl group, propyl. Examples thereof include a benzenetriyl group, a butylbenzenetriyl group, a pentabenzenetriyl group, a butylmethylbenzenetriyl group, a hydroxybenzenetriyl group, a dihydroxybenzenetriyl group, a fluoromethylbenzenetriyl group and the like.

It is a tetravalent group having 6 to 60 carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent, and the aryl group may have a substituent having 1 to 1 carbon atoms. Those having 30 linear or branched alkyl groups or hydroxyl groups are not particularly limited, but for example, methylbenzenetetrayl group, dimethylbenzenetetrayl group, trimethylbenzenetetrayl group, ethylbenzenetetrayl group, propyl. Examples thereof include a benzenetetrayl group, a butylbenzenetetrayl group, a pentabenzenetetrayl group, a butylmethylbenzenetetrayl group, a hydroxybenzenetetrayl group, a dihydroxybenzenetetrayl group, a fluoromethylbenzenetetrayl group and the like.

Of these, from the viewpoint of heat resistance, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentaphenyl group and a butylmethylphenyl group are preferable.
Among these, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a propylphenyl group and a butylphenyl group are particularly preferable from the viewpoint of availability of raw materials.

^RY in the above formula (A) is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. The alkyl group and aryl group may contain an ether bond, a ketone bond or an ester bond.

Each of the ^RTs in the above formula (A) is an independently linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms which may have a substituent. , An alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group, a thiol group, a group in which the hydrogen atom of a hydroxyl group is substituted with an acid dissociative group, and a hydroxyl group. It is a group selected from the group consisting of. Here, at least one of ^RT is a hydroxyl group. Further, n is an integer of 0 to 8 independently, where at least one of n is an integer of 1 to 8, m is an integer of 1 to 4, and k is an independent integer. Then, it is an integer of 0 to 2.

As used herein, the acid dissociable group refers to a characteristic group that is cleaved in the presence of an acid to cause a change in an alkali-soluble group or the like. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group and the like, and a phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable. The acid dissociable group may be appropriately selected from those proposed in hydroxystyrene resins used in chemically amplified resist compositions for KrF and ArF, (meth) acrylic acid resins, and the like. can. Although not limited, for example, the acid dissociative group described in JP2012-136520A is used.

（式（１）中、Ｒ^Ｚ、Ｒ^Ｙ、ｍ及びｋは、前記式（Ａ）で説明したものと同義である。
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の直鎖状、分岐状若しくは環状のアルキル基、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、カルボキシル基 又はチオール基であり、
Ｒ^４Ａは、各々独立して、水素原子又は酸解離性基であり、
ここで、Ｒ^４Ａの少なくとも１つは水素原子であり、
ｍ^６Ａは、各々独立して、０～７の整数である。）Since the compound of this embodiment has the above-mentioned structure, it has high heat resistance and high solvent solubility. Further, the compound of the present embodiment is preferably a compound represented by the following formula (1) from the viewpoint of solubility in a solvent and heat resistance.

(In the formula (1), R ^Z , ^RY , m and k are synonymous with those described in the above formula (A).
Each of R ^3A independently has a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. Aryl group, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group or a thiol group.
Each of R ^4A is a hydrogen atom or an acid dissociative group independently.
Here, at least one of R ^4A is a hydrogen atom,
m ^6A is an integer of 0 to 7 independently of each other. )

（式（１’）中、Ｒ^Ｚは、前記式（Ａ）で説明したものと同義である。）Further, from the viewpoint of solubility in a solvent and heat resistance, the compound represented by the above formula (1) is preferably a compound represented by the following formula (1') in the present embodiment.

(In the formula (1'), ^RZ is synonymous with the one described in the above formula (A).)

（式（２）中、Ｒ^３Ｂは、各々独立して、置換基を有していてもよい炭素数１～３０の直鎖状若しくは分岐状のアルキル基又は水酸基であり、ｍ^６Ｂは、１～５の整数である。）Further, from the viewpoint of heat resistance and solubility in an organic solvent, the compound represented by the above (1') is preferably a compound represented by the following formula (2) in the present embodiment.

In the formula (2), R ^3B is a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms which may independently have a substituent, and m ^6B is 1 It is an integer of ~ 5.)

Further, from the viewpoint of heat resistance and solubility in an organic solvent, specific examples of the compound represented by the formula (2) in the present embodiment are illustrated below, but are not limited to those listed here. Further, it is preferable that the compound is selected from the group represented by the following formulas (2-1) to (2-12).

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

In the above formula, R ^Z'is synonymous with R ^Z described in the above formula (A). Further, each of R ^4A is independently a hydrogen atom or an acid dissociative group, and at least one of OR ^4A is a hydroxyl group.

In the above formula, ^{RY'and RZ'are} synonymous with ^RY and ^RZ described in the above formula (A). Further, each of R ^4A is independently a hydrogen atom or an acid dissociative group, and at least one of OR ^4A is a hydroxyl group.

In the above formula, ^RT'is a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms, which may independently have a substituent. Further, m is an integer of 1 to 5. Further, each of R ^4A is independently a hydrogen atom or an acid dissociative group, and at least one of OR ^4A is a hydroxyl group.

In the above formula, ^RT'is a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms, which may independently have a substituent. Further, m is an integer of 1 to 9. Further, each of R ^4A is independently a hydrogen atom or an acid dissociative group, and at least one of OR ^4A is a hydroxyl group.

In the above formula, ^RT'is a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms, which may independently have a substituent. Further, m is an integer of 1 to 4. Further, each of R ^4A is independently a hydrogen atom or an acid dissociative group, and at least one of OR ^4A is a hydroxyl group.

In the above formula, ^RT'is a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms, which may independently have a substituent. Further, m is an integer of 1 to 8. Further, each of R ^4A is independently a hydrogen atom or an acid dissociative group, and at least one of OR ^4A is a hydroxyl group.

In the above formula, ^RT'is a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms, which may independently have a substituent. Further, m is an integer of 1 to 3. Further, each of R ^4A is independently a hydrogen atom or an acid dissociative group, and at least one of OR ^4A is a hydroxyl group.

Further, the compound represented by the formula (A) is preferably a compound having the following structure from the viewpoint of etching resistance.

In the above formula, R ^0A is synonymous with ^RY described in the above formula (A), R ^1A'is synonymous with R ^Z described in the above formula (A), and R ¹⁰ to R ¹¹ are the above formulas. It is synonymous with R ^4A described in (1).

In the above formula, R ¹⁰ to R ¹¹ have the same meaning as R ^4A described in the above formula (1). R ¹⁴ is a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms, which may independently have a substituent. m ¹⁴ is an integer of 1 to 5.

In the above formula, R ¹⁰ to R ¹¹ have the same meaning as R ^4A described in the above formula (1), and R ¹⁵ has the number of carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent. It is a monovalent group of 6 to 60, and the aryl group has a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms which may have a substituent, and the aryl group is When it has a hydroxyl group, it does not have an iodine atom and / or a methoxy group.

In the above formula, R ¹⁰ to R ¹¹ have the same meaning as R ^4A described in the above formula (1), and R ¹⁶ has the number of carbon atoms including an aryl group having 6 to 30 carbon atoms which may have a substituent. It is a divalent group of 6 to 60, and the aryl group has a linear or branched alkyl group or hydroxyl group having 1 to 30 carbon atoms which may have a substituent, and the aryl group is If it has a hydroxyl group, it does not have an iodine atom and / or a methoxy group.

In the above formula, R ¹⁰ to R ¹¹ have the same meaning as R ^4A described in the above formula (1), and R ¹⁴ is a direct group having 1 to 30 carbon atoms which may independently have a substituent. It is a chain or branched alkyl group or hydroxyl group. m ^14'is an integer of 0 to 4 independently. However, at least one m ^14'is an integer of 1 to 4.

In the above formula, R ¹⁰ to R ¹¹ have the same meaning as R ^4A described in the above formula (1), and R ¹⁴ is a direct group having 1 to 30 carbon atoms which may independently have a substituent. It is a chain or branched alkyl group or hydroxyl group. m ^14'is an integer of 1 to 4.

In the above formula, R ¹⁰ to R ¹¹ have the same meaning as R ^4A described in the above formula (1), and R ¹⁴ is a direct group having 1 to 30 carbon atoms which may independently have a substituent. It is a chain or branched alkyl group or hydroxyl group. m ^14'is an integer of 0 to 4 independently. However, at least one m ^14'is an integer of 1 to 4.

In the above formula, R ¹⁰ to R ¹¹ have the same meaning as R ^4A described in the above formula (1), and R ¹⁴ is a direct group having 1 to 30 carbon atoms which may independently have a substituent. It is a chain or branched alkyl group or hydroxyl group. m ^14'is an integer of 1 to 4.

In the above formula, R ¹⁰ and R ¹¹ have the same meaning as R ^4A described in the above formula (1). As the compound represented by the above formula, a compound having a dibenzoxanthene skeleton is preferable from the viewpoint of heat resistance.

The compound represented by the formula (A) is preferably a compound having the following structure from the viewpoint of availability of raw materials.

In the above formula, R ^0A is synonymous with ^RY described in the above formula (A), R ^1A'is synonymous with R ^Z described in the above formula (A), and R ¹⁰ , R ¹¹ and R ¹³ are synonymous. , Which is synonymous with R ^4A described in the above formula (1). The compound represented by the above formula is preferably a compound having a xanthene skeleton from the viewpoint of heat resistance.

In the above formula, R ¹⁰ , R ¹¹ and R ¹³ have the same meaning as R ^4A described in the above formula (1), and R ¹⁴ , R ¹⁵ , R ¹⁶ and m ¹⁴ and m ^14'have the same meaning as described above.

[Method for producing a compound represented by the formula (A)]
The compound represented by the formula (A) of the present embodiment can be appropriately synthesized by applying a known method, and the synthesis method is not particularly limited. For example, a compound represented by the above general formula (A) is obtained by polycondensing reaction of naphthols and aldehydes or ketones corresponding to the desired compound structure under an acid catalyst under normal pressure. be able to. Further, if necessary, it can be performed under pressure.

Examples of the naphthols include, but are not limited to, naphthol, methylnaphthol, methoxynaphthalene, naphthalenediol, naphthalenetriol and the like. These can be used alone or in combination of two or more. Among these, it is more preferable to use naphthalenediol and naphthalenetriol from the viewpoint that a xanthene structure can be easily formed.

Examples of the aldehydes include methylbenzaldehyde, dimethylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, pentabenzaldehyde, butylmethylbenzaldehyde, hydroxybenzaldehyde, dihydroxybenzaldehyde, fluoromethylbenzaldehyde and the like. Not particularly limited. These can be used alone or in combination of two or more. Among these, it is preferable to use methylbenzaldehyde, dimethylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, pentabenzaldehyde, butylmethylbenzaldehyde and the like from the viewpoint of imparting high heat resistance.

Examples of the ketones include acetylmethylbenzene, acetyldimethylbenzene, acetyltrimethylbenzene, acetylethylbenzene, acetylpropylbenzene, acetylbutylbenzene, acetylpentabenzene, acetylbutylmethylbenzene, acetylhydroxybenzene, acetyldihydroxybenzene, and acetylfluororo. Examples thereof include methylbenzene, but the present invention is not particularly limited thereto. These can be used alone or in combination of two or more. Among these, it is preferable to use acetylmethylbenzene, acetyldimethylbenzene, acetyltrimethylbenzene, acetylethylbenzene, acetylpropylbenzene, acetylbutylbenzene, acetylpentabenzene, and acetylbutylmethylbenzene from the viewpoint of imparting high heat 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. Specific examples of the above acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; Organic acids such as acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid; zinc chloride, aluminum chloride , Lewis acids such as iron chloride and boron trifluoride; solid acids such as silicate tung acid, phosphotung acid, silicate molybdic acid, phosphomolybdic acid and the like, but are not particularly limited thereto. Among these, organic acids and solid acids are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as easy availability and handling. As for the acid catalyst, one type may be used alone, or two or more types may be used in combination. The amount of the acid catalyst used can be appropriately set according to the raw material used, the type of catalyst used, reaction conditions, etc., and is not particularly limited, but is 0.01 to 100 with respect to 100 parts by mass of the reaction raw material. It is preferably parts by mass.

A reaction solvent may be used in the above reaction. The reaction solvent is not particularly limited as long as the reaction between the aldehydes or ketones used and the phenols proceeds, and can be appropriately selected from known ones, and can be used, for example, water or methanol. , Ethanol, propanol, butanol, methanol, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or a mixed solvent thereof and the like are exemplified. As the solvent, one type can be used alone, or two or more types can be used in combination. The amount of these solvents used can be appropriately set according to the raw materials used, the type of acid catalyst used, reaction conditions, and the like. The amount of the solvent used is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. Further, the reaction temperature in the above reaction can be appropriately selected according to the reactivity of the reaction raw material. The reaction temperature is not particularly limited, but is usually preferably in the range of 10 to 200 ° C. As the compound having the structure represented by the general formula (A) of the present embodiment, in order to form a xanthene structure or a thioxanthene structure, it is preferable that the reaction temperature is high, specifically, in the range of 60 to 200 ° C. Is preferable. As the reaction method, a known method can be appropriately selected and used, and the reaction method is not particularly limited, but is a method of collectively charging phenols, aldehydes or ketones, an acid catalyst, or phenols, aldehydes or ketones. There is a method of dropping in the presence of an acid catalyst. After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to a conventional method and is not particularly limited. For example, in order to remove unreacted raw materials and acid catalysts existing in the system, a general method such as raising the temperature of the reaction kettle to 130 to 230 ° C. and removing volatile substances at about 1 to 50 mmHg is used. By taking it, the desired compound can be obtained.

As preferable reaction conditions, 1 mol to excess amount of phenols and 0.001 to 1 mol of acid catalyst are used for 1 mol of aldehydes or ketones, and the pressure is 50 to 200 ° C. for 20 minutes to 20 minutes. It proceeds by reacting for about 100 hours.

After completion of the reaction, the desired product can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, the reaction product is cooled to room temperature, filtered to separate, and the solid obtained by filtration is dried, and then subjected to column chromatography. The compound having a structure represented by the above general formula (A), which is the target product, can be obtained by separating and purifying from the by-product and distilling off the solvent, filtering and drying.

The molecular weight of the compound having the structure represented by the general formula (A) is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) is preferably 350 to 30,000, more preferably 500. ~ 20,000. Further, from the viewpoint of increasing the crosslinking efficiency and suppressing the volatile components in the bake, the compound having the structure represented by the above general formula (A) has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1. Those in the range of 1 to 7 are preferable. The Mw and Mn can be measured by the method described in Examples described later.

The compound having the structure represented by the above-mentioned general formula (A) is preferably highly soluble in a solvent from the viewpoint of facilitating the application of a wet process and the like. More specifically, these compounds and / or resins have a solubility of 10% by mass or more in 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent. Is preferable. Here, the solubility in PGME and / or PGMEA is defined as "mass of resin ÷ (mass of resin + mass of solvent) × 100 (mass%)". For example, 10 g of the compound represented by the general formula (A) is evaluated to be soluble in 90 g of PGMEA when the solubility of the compound represented by the general formula (A) in PGMEA is "10% by mass or more". Yes, it is evaluated that it does not dissolve when the solubility is "less than 10% by mass".

When the underlayer film forming material for lithography of the present embodiment contains an organic solvent which is an optional component described later, the content of the compound having the structure represented by the above-mentioned general formula (A) is not particularly limited, but the organic solvent. It is preferably 1 to 33 parts by mass, more preferably 2 to 25 parts by mass, and further preferably 3 to 20 parts by mass with respect to 100 parts by mass of the total amount including.

[Resin having a structural unit derived from the compound represented by the formula (A)]
The resin of the present embodiment is a resin having a structural unit derived from the compound represented by the above formula (A) (hereinafter, also referred to as “compound of the present embodiment”). The compound represented by the above formula (A) can be used as it is as a film forming composition for lithography or the like. It can also be used as a resin having a structural unit derived from the compound represented by the above formula (A). The resin having a structural unit derived from the compound represented by the formula (A) includes a resin having a structural unit derived from the compound represented by the formula (1) and a resin represented by the formula (1'). A resin having a structural unit derived from the compound and a resin having a structural unit derived from the compound represented by the formula (2) are included. Hereinafter, the "compound represented by the formula (A)" is referred to as "a compound represented by the formula (A). It shall be read as "a compound represented by 1)", "a compound represented by the formula (1')", and "a compound represented by the formula (2)".

[Method for producing a resin having a structural unit derived from the compound represented by the formula (A)]
The resin of the present embodiment can be obtained, for example, by reacting the compound represented by the above formula (A) with a compound having a cross-linking reactivity.

As the compound having a cross-linking reaction, known compounds can be used without particular limitation as long as the compound represented by the above formula (A) can be oligomerized or polymerized. Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds and the like.

Specific examples of the resin in the present embodiment include a resin obtained by novolacizing a compound represented by the above formula (A) by a condensation reaction with an aldehyde which is a compound having a cross-linking reaction.

Here, examples of the aldehyde used for novolacizing the compound represented by the above formula (A) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, and the like. Examples thereof include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthoaldehyde, anthracenecarbaldehyde, phenanthrencarbaldehyde, pyrenecarbaldehyde, furfural and the like. Of these, formaldehyde is more preferred. In addition, these aldehydes can be used individually by 1 type or in combination of 2 or more types. The amount of the aldehydes used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 0.5 to 2 mol, based on 1 mol of the compound represented by the above formula (A). be.

An acid catalyst can also be used in the condensation reaction between the compound represented by the above formula (A) and the aldehyde. The acid catalyst used here can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, an inorganic acid, an organic acid, a Lewis acid, and a solid acid are widely known, and for example, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; Malonic acid, astringent 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, benzenesulfon Organic acids such as acids, naphthalene sulfonic acid and naphthalenedi sulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; Examples thereof include solid acids, but the present invention is not particularly limited thereto. Among these, organic acids and solid acids are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferable from the viewpoint of production such as easy availability and handling. As for the acid catalyst, one type may be used alone or two or more types may be used in combination.

The amount of the acid catalyst used can be appropriately set according to the raw material used, the type of catalyst used, reaction conditions, etc., and is not particularly limited, but is 0.01 to 100 with respect to 100 parts by mass of the reaction raw material. It is preferably parts by mass.

However, as cross-linking reactive compounds, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphtylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroinden, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene , Α-Pinene, β-Pinene, Limonen and other compounds having a non-conjugated double bond do not necessarily require aldehydes.

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

The amount of these reaction solvents used can be appropriately set according to the type of raw material used, the type of catalyst used, reaction conditions, etc., and is not particularly limited, but is 0 to 2000 mass with respect to 100 parts by mass of the reaction raw material. It is preferably in the range of parts. Further, the reaction temperature can be appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C. The reaction method can be appropriately selected and used by a known method, and is not particularly limited, but is a method of collectively charging the compound, aldehydes and catalyst represented by the above formula (A), or the above formula (A). ) Is added dropwise in the presence of a catalyst.

After completion of the polycondensation reaction, the obtained resin can be isolated according to a conventional method and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts existing in the system, a general method such as raising the temperature of the reaction kettle to 130 to 230 ° C. and removing volatile substances at about 1 to 50 mmHg is adopted. Thereby, the novolakized resin, which is the target product, can be obtained.

Here, the resin in the present embodiment may be a homopolymer of the compound represented by the above formula (A), or may be a copolymer with other phenols. Examples of the phenols that can be copolymerized here include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, and methoxyphenol. Examples thereof include propylphenol, pyrogallol, timol and the like, but the present invention is not particularly limited thereto.

In addition to the other phenols described above, the resin in this embodiment may be copolymerized with a polymerizable monomer. Examples of such copolymerization monomers include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphtylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, and 4-vinylcyclohexene. , Norbornadiene, vinylnorbornaene, pinen, limonene and the like, but are not particularly limited thereto. Even if the resin in the present embodiment is a copolymer of two or more elements (for example, a 2- to 4-element system) of the compound represented by the above formula (A) and the above-mentioned phenols, the above formula (for example) Even if it is a binary or more (for example, 2- to quaternary) copolymer of the compound represented by A) and the above-mentioned copolymerized monomer, the compound represented by the above-mentioned formula (A) and the above-mentioned phenols It may be a copolymer of 3 or more elements (for example, 3 to 4 elements) with the above-mentioned copolymerization monomer.

The molecular weight of the resin in this embodiment is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20,000. Further, from the viewpoint of increasing the crosslinking efficiency and suppressing the volatile components in the bake, the resin in the present embodiment has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) in the range of 1.2 to 7. preferable. The Mn can be obtained by the method described in Examples described later.

[Composition]
The composition of the present embodiment contains one or more substances selected from the group consisting of the compound represented by the formula (A) and a resin having a structural unit derived from the compound. Further, the composition of the present embodiment may contain both the compound of the present embodiment and the resin of the present embodiment. Hereinafter, "one or more selected from the group consisting of the compound represented by the above formula (A) and the resin having a structural unit derived from the compound" is referred to as "the compound and / or the resin of the present embodiment" or "component". Also called "(A)".

[Composition for forming optical components]
The composition for forming an optical component of the present embodiment contains at least one selected from the group consisting of a compound represented by the above formula (A) and a resin having a structural unit derived from the compound. Further, the composition for forming an optical component of the present embodiment may contain both the compound of the present embodiment and the resin of the present embodiment. Here, the "optical component" includes a film-shaped component, a sheet-shaped component, a plastic lens (prism lens, lenticular lens, microlens, frennel lens, viewing angle control lens, contrast improving lens, etc.), a retardation film, and the like. Refers to an electromagnetic wave shielding film, a prism, an optical fiber, a solder resist for flexible printed wiring, a plated resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide. The compounds and resins of the present embodiment are useful for these optical component forming applications.

[Film formation composition for lithography]
The film forming composition for lithography of the present embodiment contains one or more substances selected from the group consisting of a compound represented by the above formula (A) and a resin having a structural unit derived from the compound. Further, the lithographic film forming composition of the present embodiment may contain both the compound of the present embodiment and the resin of the present embodiment.

[Resist composition]
The resist composition of the present embodiment contains one or more substances selected from the group consisting of the compound represented by the above formula (A) and a resin having a structural unit derived from the compound. Further, the resist composition of the present embodiment may contain both the compound of the present embodiment and the resin of the present embodiment.

Further, the resist composition of the present embodiment preferably contains a solvent. The solvent is not particularly limited, but for example, 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. Classes; 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 lactate -Lactic acid esters such as butyl and n-amyl lactic acid; aliphatics such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate and ethyl propionate. Carous 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), cyclohexanone (CHN); N, N-dimethylformamide, N-methylacetamide, Amids such as N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-lactone and the like can be mentioned, but are not particularly limited. These solvents can 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, 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, but the solid component is 1 to 80% by mass and the solvent is 20 to 99% by mass with respect to the total mass of 100% by mass of the amount of the solid component and the solvent. %, More preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, still more preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably the solid component. 2 to 10% by mass and 90 to 98% by mass of the solvent.

[Other ingredients]
The resist composition of the present embodiment contains, if necessary, other components such as a cross-linking agent, an acid generator, and an organic solvent, in addition to the compound having the structure represented by the above-mentioned general formula (A). May be good. Hereinafter, these optional components will be described.

[Acid generator (C)]
In the resist composition of the present embodiment, acid is directly or indirectly generated by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray and ion beam. It is preferable to contain one or more of the acid generator (C). The acid generator (C) is not particularly limited, but for example, the acid generator (C) described in International Publication No. 2013/024778 can be used. The acid generator (C) may be used alone or in combination of two or more.

The amount of the acid generator (C) used is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, still more preferably 3 to 30% by mass, and 10 to 25% by mass based on the total weight of the solid component. Especially preferable. By using within the above range, a pattern profile with high sensitivity and low edge roughness can be obtained. In the present embodiment, if an acid is generated in the system, the method of generating the acid is not limited. Finer processing is possible by using an excimer laser instead of ultraviolet rays such as g-rays and i-rays, and further fine processing is possible by using electron beams, extreme ultraviolet rays, X-rays, and ion beams as high-energy rays. Is possible.

[Acid cross-linking agent (G)]
In the present embodiment, it is preferable to contain one or more acid cross-linking agents (G). The acid cross-linking agent (G) is a compound capable of intramolecularly or intermolecularly cross-linking the component (A) in the presence of an acid generated from the acid generator (C). Examples of such an acid cross-linking agent (G) include compounds having one or more groups (hereinafter, referred to as “crosslinkable groups”) capable of cross-linking the component (A).

Such a crosslinkable group is not particularly limited, but is, for example, (i) hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group), acetoxy (C1-C6 alkyl group) and the like. Alkyl group or group derived from them; (ii) carbonyl group such as formyl group, carboxy (C1-C6 alkyl group) or group derived from them; (iii) dimethylaminomethyl group, diethylaminomethyl group, dimethylol Nitrogen-containing group-containing group such as aminomethyl group, dietylolaminomethyl group, morpholinomethyl group; (iv) glycidyl group-containing group such as glycidyl ether group, glycidyl ester group, glycidylamino group; (v) benzyloxymethyl group, Groups derived from aromatic groups such as C1-C6 allyloxy (C1-C6 alkyl group), C1-C6 aralkyloxy (C1-C6 alkyl group), such as benzoyloxymethyl group; (vi) vinyl group, isopropenyl Examples thereof include a polymerizable multiple bond-containing group such as a group. As the crosslinkable group of the acid crosslinking agent (G) in the present embodiment, a hydroxyalkyl group, an alkoxyalkyl group and the like are preferable, and an alkoxymethyl group is particularly preferable.

The acid cross-linking agent (G) having a cross-linking group is not particularly limited, but for example, the one described in International Publication No. 2013/024778 can be used. The acid cross-linking agent (G) can be used alone or in combination of two or more.

In the present embodiment, the amount of the acid cross-linking agent (G) used is preferably 0.5 to 49% by mass, more preferably 0.5 to 40% by mass, still more preferably 1 to 30% by mass, based on the total weight of the solid component. 2 to 20% by mass is particularly preferable. When the blending ratio of the acid cross-linking agent (G) is 0.5% by mass or more, the effect of suppressing the solubility of the resist film in the alkaline developer is improved, the residual film ratio is lowered, and the pattern is swollen or tortuous. It is preferable because it can suppress the occurrence, and on the other hand, when it is 50% by mass or less, it is preferable because the decrease in heat resistance as a resist can be suppressed.

[Acid diffusion control agent (E)]
In the present embodiment, the acid diffusion control agent (E) has an action of controlling the diffusion of the acid generated from the acid generator in the resist film by irradiation to prevent an unfavorable chemical reaction in an unexposed region. May be blended into the resist composition. By using such an acid diffusion control agent (E), the storage stability of the resist composition is improved. In addition, the resolution is improved, and changes in the line width of the resist pattern due to fluctuations in the leaving time before irradiation and the leaving time after irradiation can be suppressed, resulting in extremely excellent process stability. The acid diffusion control agent (E) is not particularly limited, and examples thereof include radiolytic basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.

The acid diffusion control agent (E) is not particularly limited, but for example, the acid diffusion control agent (E) described in International Publication No. 2013/024778 can be used. The acid diffusion control agent (E) may be used alone or in combination of two or more.

The blending amount of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.01 to 5% by mass, and 0. 0.01 to 3% by mass is particularly preferable. Within the above range, it is possible to prevent deterioration of resolution, pattern shape, dimensional fidelity, and the like. Further, even if the leaving time from the electron beam irradiation to the heating after the irradiation is long, the shape of the upper layer portion of the pattern does not deteriorate. Further, when the blending amount is 10% by mass or less, it is possible to prevent deterioration of sensitivity, developability of the unexposed portion and the like. Further, by using such an acid diffusion control agent, the storage stability of the resist composition is improved, the resolution is improved, and the retention time before irradiation and the retention time after irradiation fluctuate. The change in the line width of the resist pattern can be suppressed, and the process stability is extremely excellent.

[Other ingredients (F)]
In the resist composition of the present embodiment, as other components (F), a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant, an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof, if necessary. It is possible to add one kind or two or more kinds of various additives such as.

[Dissolution accelerator]
When the solubility of the compound represented by the formula (A) in the developing solution is too low, the low molecular weight dissolution accelerator enhances the solubility and moderately increases the dissolution rate of the compound during development. It is a component that has and can be used as needed. Examples of the dissolution accelerator include low molecular weight phenolic compounds, and examples thereof include bisphenols and tris (hydroxyphenyl) methane. These dissolution accelerators can be used alone or in admixture of two or more.

The blending amount of the dissolution accelerator is appropriately adjusted according to the type of the above compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total weight of the solid component. Is more preferable, and 0% by mass is particularly preferable.

[Dissolution control agent]
The dissolution control agent is a component having an action of controlling the solubility of the compound represented by the formula (A) in a developing solution and appropriately reducing the dissolution rate during development. As such a dissolution control agent, one that does not chemically change in steps such as firing of the resist film, irradiation, and development is preferable.

The dissolution control agent is not particularly limited, and for example, aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthylketone; Sulfones and the like can be mentioned. These dissolution control agents may be used alone or in combination of two or more.
The blending amount of the dissolution control agent is appropriately adjusted according to the type of the above compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total weight of the solid component. Is more preferable, and 0% by mass is particularly preferable.

[Sensitizer]
The sensitizer has the effect of absorbing the energy of the irradiated radiation and transferring that energy to the acid generator (C), thereby increasing the amount of acid produced, improving the apparent sensitivity of the resist. It is an ingredient that causes. Examples of such a sensitizer include benzophenones, biacetyls, pyrenes, phenothiazines, fluorenes and the like, but are not particularly limited. These sensitizers can be used alone or in combination of two or more.

The blending amount of the sensitizer is appropriately adjusted according to the type of the above compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total weight of the solid component. More preferably, 0% by mass is particularly preferable.

[Surfactant]
The surfactant is a component having an action of improving the coatability, striation, developability of the resist, etc. of the resist composition of the present embodiment. Such a surfactant may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant or an amphoteric surfactant. Preferred surfactants are nonionic surfactants. The nonionic surfactant has a good affinity with the solvent used for producing the resist composition and is more effective. Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyethylene glycol higher fatty acid diesters, and the like, but are not particularly limited. The commercial products are not particularly limited, but the following product names include, for example, Ftop (manufactured by Gemco), Megafuck (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, and Surflon (manufactured by Sumitomo 3M). As mentioned above, examples thereof include Asahi Glass Co., Ltd.), Pepole (Toho Chemical Industry Co., Ltd.), KP (Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (Kyoei Co., Ltd. Oil and Fat Chemical Industry Co., Ltd.) and the like.

The blending amount of the surfactant is appropriately adjusted according to the type of the above compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total weight of the solid component. Is more preferable, and 0% by mass is particularly preferable.

[Organic carboxylic acid or phosphorus oxoacid or its derivative]
For the purpose of preventing deterioration of sensitivity or improving the shape of the resist pattern, retention stability, etc., an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be further contained as an arbitrary component. The organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof can be used in combination with an acid diffusion control agent, or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Examples of the oxo acid of phosphorus or a derivative thereof include phosphoric acid such as phosphoric acid, di-n-butyl ester of phosphoric acid, diphenyl ester of phosphoric acid, or a derivative of such ester, phosphonic acid, dimethyl phosphonic acid ester, and di-phosphonic acid di-. Examples thereof include phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester and phosphonic acid dibenzyl ester or derivatives such as their esters, phosphinic acid such as phosphinic acid and phenylphosphinic acid and derivatives such as their esters. Of these, phosphonic acid is particularly preferable.

The organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof may be used alone or in combination of two or more. The blending amount of the organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof is appropriately adjusted according to the type of the above compound used, but is preferably 0 to 49% by mass, preferably 0 to 5% by mass, based on the total weight of the solid component. More preferably, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.

[Other additives other than the above-mentioned additives (dissolution accelerator, dissolution control agent, sensitizer, surfactant, organic carboxylic acid or phosphorus oxo acid or its derivative, etc.)]
Further, the resist composition of the present embodiment contains, if necessary, a dissolution control agent, a sensitizer, a surfactant, and an additive other than the organic carboxylic acid or phosphorus oxoacid or a derivative thereof. Alternatively, two or more types can be blended. Examples of such additives include dyes, pigments, adhesive aids and the like. For example, it is preferable to add a dye or a pigment because the latent image of the exposed portion can be visualized and the influence of halation during exposure can be alleviated. Further, it is preferable to add an adhesive aid because the adhesiveness to the substrate can be improved. Further, the other additives are not particularly limited, and examples thereof include anti-halation agents, storage stabilizers, antifoaming agents, shape improvers, and the like, specifically, 4-hydroxy-4'-methylchalcone and the like. Can be done.

In the resist composition of the present embodiment, the total amount of the optional component (F) is 0 to 99% by mass, preferably 0 to 49% by mass, more preferably 0 to 10% by mass, and 0. It is more preferably from 5% by mass, still more preferably from 0 to 1% by mass, and particularly preferably from 0% by mass.

[Mixing ratio of each component in the resist composition]
In the resist composition of the present embodiment, the content of the compound and / or the resin of the present embodiment is not particularly limited, but is represented by the total mass of the solid component (compound represented by the formula (A), represented by the formula (A)). Resin containing the compound as a constituent, acid generator (C), acid cross-linking agent (G), acid diffusion control agent (E) and other components (F) (also referred to as "arbitrary component (F)"), etc. 50 to 99.4% by mass, more preferably 55 to 90% by mass, still more preferably 60 to 80% by mass, based on the total amount of the solid components including the components arbitrarily used. Particularly preferably, it is 60 to 70% by mass. In the case of the above content, the resolution is further improved and the line edge roughness (LER) is further reduced. When both the compound and the resin of the present embodiment are contained, the above-mentioned content is the total amount of the compound and the resin of the present embodiment.

In the resist composition of the present embodiment, the compound and / or the resin of the present embodiment (component (A)), acid generator (C), acid cross-linking agent (G), acid diffusion control agent (E), optional component ( The content ratio of F) (component (A) / acid generator (C) / acid cross-linking agent (G) / acid diffusion control agent (E) / optional component (F)) is 100% by mass of solid content of the resist composition. %, It is preferably 50 to 99.4% by mass / 0.001 to 49% by mass / 0.5 to 49% by mass / 0.001 to 49% by mass / 0 to 49% by mass, and more preferably. 55 to 90% by mass / 1 to 40% by mass / 0.5 to 40% by mass / 0.01 to 10% by mass / 0 to 5% by mass, more preferably 60 to 80% by mass / 3 to 30% by mass. It is / 1 to 30% by mass / 0.01 to 5% by mass / 0 to 1% by mass, and particularly preferably 60 to 70% by mass / 10 to 25% by mass / 2 to 20% by mass / 0.01 to 3% by mass. % / 0% by mass. The blending ratio of the components is selected from each range so that the total of the components is 100% by mass. With the above formulation, the performance such as sensitivity, resolution, and developability is excellent. The "solid content" means a component excluding the solvent, and the "solid content 100% by mass" means that the component excluding the solvent is 100% by mass.

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

The resist composition of the present embodiment may contain a resin other than the resin of the present embodiment, if necessary. The resin is not particularly limited, and is, for example, a weight containing novolak resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol, or vinylphenol as a monomer unit. Phenol or derivatives thereof may be mentioned. The content of the resin is not particularly limited and is appropriately adjusted according to the type of the component (A) used, but is preferably 30 parts by mass or less, more preferably 30 parts by mass with respect to 100 parts by mass of the component (A). It is 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.

[Physical characteristics of resist composition, etc.]
The resist composition of the present embodiment can form an amorphous film by spin coating. It can also 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 produced separately.

In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition of the present embodiment in a developing solution at 23 ° C. is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec. It is preferably 0.0005 to 5 Å / sec, more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developing solution and can be used as a resist. Further, if the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. It is presumed that this is because the contrast between the exposed portion that dissolves in the developing solution and the unexposed portion that does not dissolve in the developing solution increases due to the change in the solubility of the component (A) before and after exposure. In addition, it has the effects of reducing LER and reducing defects.

In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition of the present embodiment in a developing solution at 23 ° C. is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developing solution and is more suitable for a resist. Further, if the dissolution rate is 10 Å / sec or more, the resolution may be improved. It is presumed that this is because the micro surface portion of the component (A) is dissolved and the LER is reduced. It also has the effect of reducing defects.

The dissolution rate is measured 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 by a known method such as visual inspection, ellipsometer or quartz crystal vibration microbalance method (QCM method). Can be decided.

In the case of a positive resist pattern, the amorphous film formed by spin-coating the resist composition of the present embodiment with respect to the developing solution at 23 ° C. of the portion exposed to radiation such as KrF excimer laser, extreme ultraviolet rays, electron beam or X-ray. The dissolution rate is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developing solution and is more suitable for a resist. Further, if the dissolution rate is 10 Å / sec or more, the resolution may be improved. It is presumed that this is because the micro surface portion of the component (A) is dissolved and the LER is reduced. It also has the effect of reducing defects.

In the case of a negative resist pattern, the amorphous film formed by spin-coating the resist composition of the present embodiment with respect to the developing solution at 23 ° C. of the portion exposed by radiation such as KrF excimer laser, extreme ultraviolet rays, electron beam or X-ray. The dissolution rate is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, still more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developing solution and can be used as a resist. Further, if the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. It is presumed that this is because the contrast between the unexposed portion that dissolves in the developing solution and the exposed portion that does not dissolve in the developing solution increases due to the change in the solubility of the component (A) before and after exposure. It also has the effect of reducing LER and reducing defects.

[Radiation-sensitive composition]
The radiation-sensitive composition of the present embodiment contains the compound of the present embodiment and / or the resin of the present embodiment (component (A)), a diazonaphthoquinone photoactive compound (B), and a solvent. In the sexual composition, the content of the solvent is 20 to 99% by mass with respect to the total amount of 100% by mass of the radiation-sensitive composition, and the content of components other than the solvent is the radiation-sensitive. It is 1 to 80% by mass with respect to 100% by mass of the total amount of the sex composition.

The component (A) contained in the radiation-sensitive composition of the present embodiment is used in combination with the diazonaphthoquinone photoactive compound (B) described later, and g-ray, h-ray, i-ray, KrF excimer laser, ArF excimer laser, and extreme. It is useful as a base material for a positive resist, which becomes a compound easily soluble in a developing solution by irradiating with ultraviolet rays, electron beams, or X-rays. Diazonaphthoquinone photoactivity that is sparingly soluble in the developing solution, although the properties of component (A) do not change significantly with g-rays, h-rays, i-rays, KrF excimer lasers, ArF excimer lasers, extreme ultraviolet rays, electron beams, or X-rays. By changing the compound (B) into an easily soluble compound, a resist pattern can be formed by the development step.

As the component (A) contained in the radiation-sensitive composition of the present embodiment is a compound having a relatively low molecular weight as shown in the above formula (A), the roughness of the obtained resist pattern is very small.

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

The calorific value for crystallization determined by differential scanning calorimetry of the glass transition temperature of the 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, still more preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the calorific value for crystallization is less than 20 J / g, or (crystallization temperature)-(glass transition temperature) is within the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition. The film-forming property required for the resist can be maintained for a long period of time, and the resolution can be improved.

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

The component (A) contained in the radiation-sensitive composition of the present embodiment is 100 or less, preferably 120 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 140 ° C. or lower, and particularly preferably 150 ° C. or lower under normal pressure. It is preferable that the sublimation property is low. Low sublimation 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. Due to the low sublimation property, it is possible to prevent contamination of the exposure apparatus due to outgas during exposure. In addition, a good pattern shape can be obtained with low roughness.

The 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. , Anisol, butyl acetate, ethyl propionate and ethyl lactate, and in a solvent having the highest dissolving ability for the component (A) at 23 ° C., preferably 1% by mass or more, more preferably 5% by mass. % Or more, more preferably 10% by mass or more, and even more preferably, in a solvent selected from PGMEA, PGME, CHN and exhibiting the highest dissolving ability for the component (A) at 23 ° C., 20 It dissolves in an amount of 20% by mass or more, particularly preferably 20% by mass or more at 23 ° C. with PGMEA. By satisfying the above conditions, it can be used in 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 containing a polymeric and non-polymeric diazonaphthoquinone photoactive compound, and is generally used in a positive resist composition. As long as it is used as a photosensitive component (photosensitive agent), there is no particular limitation, and one type or two or more types can be arbitrarily selected and used.

Such a photosensitizer was obtained by reacting naphthoquinone diazide sulfonic acid chloride, benzoquinone diazido sulfonic acid chloride, or the like with a low molecular weight compound or a high molecular weight compound having a functional group capable of condensing with these acid chlorides. Compounds are preferred. Here, the functional group that can be condensed with the acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, but a hydroxyl group is particularly preferable. The compound capable of condensing with the acid chloride containing a hydroxyl group is not particularly limited, and is, for example, hydroquinone, resorcin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and the like. 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 , 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 can be mentioned.

Further, as the acid chloride such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazido sulfonic acid chloride, for example, 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazido-4-sulfonyl chloride and the like are preferable. Can be mentioned.

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

[solvent]
The solvent that can be used in the radiation-sensitive composition of the present embodiment is not particularly limited, and is, for example, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, cyclopentanone, 2-heptanone, anisole, and butyl acetate. , Ethyl propionate, and ethyl lactate. Of these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone are preferable, and the solvent may be used alone or in combination of two or more.

The content of the solvent is 20 to 99% by mass, preferably 50 to 99% by mass, more preferably 60 to 98% by mass, particularly, with respect to 100% by mass of the total amount of the radiation-sensitive composition. It is preferably 90 to 98% by mass.

The content of the component (solid component) other than the solvent is 1 to 80% by mass, preferably 1 to 50% by mass, more preferably 1 to 50% by mass, based on 100% by mass of the total amount of the radiation-sensitive composition. It is 2 to 40% by mass, and particularly preferably 2 to 10% by mass.

[Characteristics of radiation-sensitive composition]
The radiation-sensitive composition of the present embodiment can form an amorphous film by spin coating. It can also 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 produced separately.

In the case of the positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment in a developing solution at 23 ° C. is preferably 5 Å / sec or less, preferably 0.05 to 5 Å / sec. Is more preferable, and 0.0005 to 5 Å / sec is even more preferable. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developing solution and can be used as a resist. Further, if the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. It is presumed that this is because the contrast between the exposed portion that dissolves in the developing solution and the unexposed portion that does not dissolve in the developing solution increases due to the change in the solubility of the component (A) before and after exposure. It also has the effect of reducing LER and reducing defects.

In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment in a developing solution at 23 ° C. is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developing solution and is more suitable for a resist. Further, if the dissolution rate is 10 Å / sec or more, the resolution may be improved. It is presumed that this is because the micro surface portion of the component (A) is dissolved and the LER is reduced. It also has the effect of reducing defects.

The dissolution rate can be determined by immersing the amorphous film in a developing solution at 23 ° C. and measuring the film thickness before and after the immersion by a known method such as visual inspection, ellipsometer or QCM method.

In the case of the positive resist pattern, after irradiating the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment with radiation such as KrF excimer laser, extreme ultraviolet rays, electron beam or X-ray, or from 20 to 20. The dissolution rate of the exposed portion after heating at 500 ° C. in the developing solution at 23 ° C. is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, still more preferably 100 to 1000 Å / sec. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developing solution and is more suitable for a resist. Further, if the dissolution rate is 10,000 Å / sec or less, the resolution may be improved. It is presumed that this is because the micro surface portion of the component (A) is dissolved and the LER is reduced. It also has the effect of reducing defects.
In the case of a negative resist pattern, after irradiation with radiation such as KrF excimer laser, extreme ultraviolet rays, electron beam or X-ray of an amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment, or from 20 to 20. The dissolution rate of the exposed portion after heating at 500 ° C. in the developing solution at 23 ° C. is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, still more preferably 0.0005 to 5 Å / sec. .. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developing solution and can be used as a resist. Further, if the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. It is presumed that this is because the contrast between the unexposed portion that dissolves in the developing solution and the exposed portion that does not dissolve in the developing solution increases due to the change in the solubility of the component (A) before and after exposure. It also has the effect of reducing LER and reducing defects.

[Mixing ratio of each component in the radiation-sensitive composition]
In the radiation-sensitive composition of the present embodiment, the content of the component (A) is arbitrarily used such as the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B) and other components (D)). It is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass with respect to the total amount of the solid components to be produced (the same applies hereinafter). %. In the radiation-sensitive composition of the present embodiment, when the content of the component (A) is within the above range, a pattern with high sensitivity and small roughness can be obtained.

In the radiation-sensitive composition of the present embodiment, the content of the diazonaphthoquinone photoactive compound (B) is the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc. 1 to 99% by weight, more preferably 5 to 95% by weight, still more preferably 10 to 90% by weight, and particularly preferably 10 to 90% by weight, based on the total of the solid components arbitrarily used in the above. It is 25 to 75% by weight. When the content of the diazonaphthoquinone photoactive compound (B) is within the above range, the radiation-sensitive composition of the present embodiment can obtain a pattern with high sensitivity and small roughness.

[Other ingredients (D)]
In the radiation-sensitive composition of the present embodiment, if necessary, as components other than the component (A) and the diazonaphthoquinone photoactive compound (B), the above-mentioned acid generator, acid cross-linking agent, acid diffusion control agent, etc. One or two or more kinds of additives such as a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant, an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof can be added. In addition, in this specification, the other component (D) may be referred to as an optional component (D).

Content ratio ((A) / (B) / ( D)) is preferably 1 to 99% by mass / 99 to 1% by mass / 0 to 98% by mass, and more preferably 5 to 95% by mass with respect to 100% by mass of the solid content of the radiation-sensitive composition. / 95 to 5% by mass / 0 to 49% by mass, more preferably 10 to 90% by mass / 90 to 10% by mass / 0 to 10% by mass, and particularly preferably 20 to 80% by mass / 80 to 20%. It is mass% / 0 to 5% by mass, and most preferably 25 to 75% by mass / 75 to 25% by mass / 0% by mass.

The blending ratio of each component is selected from each range so that the total is 100% by mass. The radiation-sensitive composition of the present embodiment is excellent in performance such as sensitivity and resolution in addition to roughness when the blending ratio of each component is within the above range.

The radiation-sensitive composition of the present embodiment may contain a resin other than the present embodiment. Such resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and polymers containing acrylic acid, vinyl alcohol, or vinylphenol as a monomer unit, or polymers thereof. Examples include derivatives. The blending amount of these resins is appropriately adjusted according to the type of the component (A) used, but is preferably 30 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the component (A). It is more preferably 5 parts by mass or less, and particularly preferably 0 part by mass.

[Manufacturing method of amorphous film]
The method for producing an amorphous film of the present embodiment includes a step of forming an amorphous film on a substrate by using the above-mentioned radiation-sensitive composition.

[Method for forming a resist pattern using a radiation-sensitive composition]
The resist pattern forming method using the radiation-sensitive composition of the present embodiment includes a step of forming a resist film on a substrate using the above-mentioned radiation-sensitive composition and at least a part of the formed resist film. It includes a step of exposing and a step of developing the exposed resist film to form a resist pattern. In detail, the same operation as the following resist pattern forming method using a resist composition can be performed.

[Method for forming a resist pattern using a resist composition]
The method for forming a resist pattern using the resist composition of the present embodiment includes a step of forming a resist film on a substrate using the resist composition of the present embodiment described above, and at least a part of the formed resist film. It includes a step of exposing and a step of developing the exposed resist film to form a resist pattern. The resist pattern in this embodiment can also be formed as an upper resist in a multilayer process.

The method for forming the resist pattern is not particularly limited, and examples thereof include the following methods. First, a resist film is formed by applying the resist composition of the present embodiment on a conventionally known substrate by a coating means such as rotary coating, cast coating, and roll coating. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, the present invention is not particularly limited, and examples thereof include a silicon wafer, a metal substrate such as copper, chromium, iron, and aluminum, and a glass substrate. The material of the wiring pattern is not particularly limited, and examples thereof include copper, aluminum, nickel, and gold. Further, if necessary, an inorganic and / or organic film may be provided on the above-mentioned substrate. The inorganic film is not particularly limited, and examples thereof include an inorganic antireflection film (inorganic BARC). The organic film is not particularly limited, and examples thereof include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.

Next, if necessary, the coated substrate is heated. The heating conditions vary depending on the composition of the resist composition and the like, but are preferably 20 to 250 ° C, more preferably 20 to 150 ° C. By heating, the adhesion of the resist to the substrate may be improved, which is preferable. The resist film is then exposed to the desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer lasers, electron beams, extreme ultraviolet rays (EUV), X-rays, and ion beams. The exposure conditions and the like are appropriately selected according to the compounding composition and the like of the resist composition. In the present embodiment, it is preferable to heat after irradiation in order to stably form a high-precision fine pattern in exposure.

Then, the exposed resist film is developed with a developing solution to form a predetermined resist pattern. As the developing solution, it is preferable to select a solvent having a solubility parameter (SP value) close to that of the component (A) to be used, and a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. A polar solvent such as, a hydrocarbon solvent, or an alkaline aqueous solution can be used.

The ketone solvent is not particularly limited, but for example, 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone. , Phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like.

The ester solvent is not particularly limited, but for example, 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. Acetic acid, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formic acid, ethyl forerate, butyl forerate, propyl forerate, ethyl lactate, butyl lactate, propyl lactate, etc. be able to.

The alcohol-based solvent is not particularly limited, but for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, etc. Alcohols such as n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol-based solvents such as ethylene glycol, diethylene glycol and triethylene glycol, and ethylene glycol monomethyl. Examples thereof include glycol ether-based solvents such as ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol.

The ether solvent is not particularly limited, and examples thereof include dioxane, tetrahydrofuran and the like in addition to the above glycol ether solvent.

The amide-based solvent is not particularly limited, but is, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-. Imidazolidinone etc. can be used.

The hydrocarbon solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, and decane.

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water as long as the solvent has performance. However, in order to fully exert the effect of the present invention, the water content of the developer as a whole is preferably less than 70% by mass, preferably less than 50% by mass, and more preferably less than 30% by mass. It is preferable that it is less than 10% by mass, and it is particularly preferable that it contains substantially no water. That is, the content of the organic solvent in the developing solution is preferably 30% by mass or more and 100% by mass or less, preferably 50% by mass or more and 100% by mass or less, and 70% by mass or more and 100% by mass, based on the total amount of the developing solution. It is more preferably 90% by mass or more, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

The alkaline aqueous solution is not particularly limited, and is, for example, mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline. Alkaline compounds such as.

In particular, the developing solution contains at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent, and the developing solution contains the resolution and roughness of the resist pattern. It is preferable because it improves the resist performance of the solvent.

The vapor pressure of the developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By reducing the vapor pressure of the developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity in the wafer surface is improved, and as a result, the dimensional uniformity in the wafer surface is improved. To improve.

Specific examples having a vapor pressure of 5 kPa or less are not particularly limited, but 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, and methylcyclohexanone. , Phenylacetone, methylisobutylketone and other ketone solvents; 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-ethoxypropio Ester-based solvents such as Nate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl forerate, propyl forirate, ethyl lactate, butyl lactate, propyl lactate; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol , Se-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 solvents; ethylene glycol, Glycol solvents such as diethylene glycol and triethylene glycol; glycols such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethylbutanol. Ether solvent; Ether solvent such as tetrahydrofuran; N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide amide solvent; Aromatic hydrocarbon solvent such as toluene and xylene, octane , Decane and other aliphatic hydrocarbon solvents can be mentioned.

Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, and methylcyclohexanone. , Phenylacetone and other ketone solvents; 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 solvents; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol Glycol ether solvents such as monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol; N-methyl-2-pyrrolidone, N, N-dimethylacetamide , N, N-dimethylformamide amide solvent; aromatic hydrocarbon solvent such as xylene; aliphatic hydrocarbon solvent such as octane and decane.

An appropriate amount of a surfactant can be added to the developing solution, if necessary.
The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used. Examples of these fluorine and / or silicon-based surfactants include Japanese Patent Application Laid-Open No. 62-36663, Japanese Patent Application Laid-Open No. 61-226746, Japanese Patent Application Laid-Open No. 61-226745, and Japanese Patent Application Laid-Open No. 62-170950. , JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the same 5360692, 5529881, 5296330, 5436098, 5576143, 5294511, and 5824451 can be mentioned. It can be, preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.

The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developing solution.

The developing method is not particularly limited, but for example, a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), or a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time. A method of developing (paddle method), a method of spraying the developer on the surface of the substrate (spray method), a method of spraying the developer on the substrate rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed. A method (dynamic dispense method) or the like can be applied. The time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

Further, after the step of performing the development, a step of stopping the development may be carried out while substituting with another solvent.

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

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

Here, examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols, and specific examples thereof are not limited, but 1-butanol and 2 -Butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol , Cyclopentanol, 2-Heptanol, 2-Octanol, 3-Hexanol, 3-Heptanol, 3-Octanol, 4-Octanol and the like can be used, and a particularly preferable monohydric alcohol having 5 or more carbon atoms is 1-. Hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like can be used.

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

The water content in the rinsing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.

The vapor pressure of the rinse solution 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 most preferably 0.12 kPa or more and 3 kPa or less at 20 ° C. By setting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, and the swelling caused by the infiltration of the rinsing liquid is further suppressed, and the dimensions in the wafer surface are further suppressed. The uniformity is improved.

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

In the rinsing step, the developed wafer is washed with the rinsing liquid containing the above organic solvent. The method of cleaning treatment is not particularly limited, but for example, a method of continuously applying a rinse solution onto a substrate rotating at a constant speed (rotational coating method), or a method of immersing the substrate in a tank filled with the rinse solution for a certain period of time. A method (dip method), a method of spraying a rinse solution on the surface of the substrate (spray method), etc. can be applied. Among them, the cleaning treatment is performed by the rotation coating method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.

A patterned wiring board is obtained by forming a resist pattern and then etching it. The etching method can be a known method such as dry etching using plasma gas and wet etching with an alkaline solution, a cupric chloride solution, a ferric chloride solution or the like.

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

The residual resist pattern after etching can be peeled off with an organic solvent. The organic solvent is not particularly limited, and examples thereof include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). The peeling method is not particularly limited, and examples thereof include a dipping method and a spray method. Further, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small-diameter through hole.

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

[Underlayer film forming material for lithography]
The lithographic underlayer film forming material of the present embodiment contains the compound of the present embodiment and / or the resin of the present embodiment. The compound of the present embodiment and / or the resin of the present embodiment is preferably 1 to 100% by mass, preferably 10 to 100% by mass, in the underlayer film forming material for lithography from the viewpoint of coatability and quality stability. It is more preferably 50 to 100% by mass, and particularly preferably 100% by mass.

The underlayer film forming material for lithography of the present embodiment can be applied to a wet process, and has excellent heat resistance and etching resistance. Further, since the material for forming the underlayer film for lithography of the present embodiment uses the above-mentioned substance, deterioration of the film during high-temperature baking is suppressed, and it is possible to form an underlayer film having excellent etching resistance to oxygen plasma etching and the like. can. Further, since the underlayer film forming material for lithography of the present embodiment has excellent adhesion to the resist layer, an excellent resist pattern can be obtained. The lithographic underlayer film forming material of the present embodiment may include already known lithographic underlayer film forming materials and the like as long as the effects of the present invention are not impaired.

[Composition for forming an underlayer film for lithography]
The composition for forming an underlayer film for lithography of the present embodiment contains the above-mentioned material for forming an underlayer film for lithography and a solvent.

[solvent]
As the solvent used in the composition for forming an underlayer film for lithography of the present embodiment, a known solvent can be appropriately used as long as the above-mentioned component (A) is at least soluble.

Specific examples of the solvent are not particularly limited, but for example, a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; a cellosolve solvent 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; alcohol solvents such as methanol, ethanol, isopropanol and 1-ethoxy-2-propanol; toluene, xylene , Aromatic hydrocarbons such as anisole and the like. These solvents may be used alone or in combination of two or more.

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

The content of the solvent is not particularly limited, but is preferably 100 to 10,000 parts by mass, more preferably 200 to 5, with respect to 100 parts by mass of the underlayer film forming material from the viewpoint of solubility and film formation. It is more preferably 000 parts by mass, and even more preferably 200 to 1,000 parts by mass.

[Crosslinking agent]
The composition for forming an underlayer film for lithography of the present embodiment may contain a cross-linking agent, if necessary, from the viewpoint of suppressing intermixing and the like. The cross-linking agent that can be used in this embodiment is not particularly limited, but for example, the one described in International Publication No. 2013/024779 can be used. In this embodiment, the cross-linking agent may be used alone or in combination of two or more.

Specific examples of the cross-linking agent that can be used in the present embodiment include phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycol uryl compounds, urea compounds, and isocyanates. Examples thereof include compounds and azide compounds, but the present invention is not particularly limited thereto. These cross-linking agents may be used alone or in combination of two or more. Among these, a benzoxazine compound, an epoxy compound or a cyanate compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improving etching resistance.

As the phenol compound, known ones can be used. For example, the phenols are not particularly limited, but in addition to phenols, alkylphenols such as cresols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalenediol, bisphenol A, and the like. Examples thereof include bisphenols such as bisphenol F, and polyfunctional phenol compounds such as phenol novolak and phenol aralkyl resins. Of these, the aralkyl-type phenol resin is preferable from the viewpoint of heat resistance and solubility.

As the epoxy compound, known ones can be used, and a compound having two or more epoxy groups in one molecule is selected. Although not particularly limited, for example, bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2'-biphenol, 3,3', 5,5 Epoxidized products of divalent phenols such as'-tetramethyl-4,4'-dihydroxybiphenol, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4). -Trivalents such as hydroxyphenyl) ethane, tris (2,3-epoxypropyl) isocyanurate, trimethylolmethanetriglycidyl ether, trimethylolpropanetriglycidyl ether, trimethylolethanetriglycidyl ether, phenol novolac, o-cresol novolac, etc. The above phenolic epoxidates, dicyclopentadiene and phenol cocondensate resin epoxidates, phenol aralkyl resins epoxidized from phenols and paraxylylene chloride, etc., phenols and bischloromethylbiphenyl, etc. Examples thereof include epoxidates of biphenyl aralkyl type phenolic resins synthesized from naphthols and epoxidates of naphthol aralkyl resins synthesized from naphthols and paraxylylene chloride. These epoxy resins may be used alone or in combination of two or more. A solid epoxy resin at room temperature, such as an epoxy resin obtained from phenol aralkyl resins and biphenyl aralkyl resins, is preferable from the viewpoint of heat resistance and solubility.

The cyanate compound is not particularly limited as long as it is a compound having two or more cyanate groups in one molecule, and known compounds can be used. In the present embodiment, a preferable cyanate compound has 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. Further, the cyanate compound preferably has an aromatic group, and a compound having a structure in which the cyanate group is directly linked to the aromatic group can be preferably used. Such cyanate compounds are not particularly limited, but are, for example, bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolak resin, cresol novolak resin, dicyclopentadiene novolak resin, tetramethylbisphenol F, bisphenol. A novolak resin, brominated bisphenol A, brominated phenol novolak resin, trifunctional phenol, tetrafunctional phenol, naphthalene type phenol, biphenyl type phenol, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, fat Examples thereof include those having a structure in which hydroxyl groups such as cyclic phenol and phosphorus-containing phenol are substituted with cyanate groups. These cyanate compounds may be used alone or in combination of two or more as appropriate. Further, the cyanate compound may be in any form of a monomer, an oligomer or a resin.

The amino compound is not particularly limited, and is, for example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 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-trizine, m-trizine, 4,4'-diaminobenzanilide, 2,2'-bis (trifluoromethyl) Examples thereof include -4,4'-diaminobiphenyl, 4-aminophenyl-4-aminobenzoate, 2- (4-aminophenyl) -6-aminobenzoxazole and the like. Furthermore, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Sulfur, 3,3'-diaminodiphenyl sulfone, 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) biphenyl] ) Benzene] ether, aromatic amines such as 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] Alicyclic amines such as decane, 1,3-bisaminomethylcyclohexane, isophoronediamine, aliphatic amines such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylenetriamine, triethylenetetramine, etc. Can be mentioned.

The benzoxazine compound is not particularly limited, but is, for example, Pd-type benzoxazine obtained from bifunctional diamines and monofunctional phenols, and F- obtained from monofunctional diamines and bifunctional phenols. Examples thereof include type a benzoxazine.

Specific examples of the melamine compound are not particularly limited, but for example, a compound in which 1 to 6 methylol groups of hexamethylol melamine, hexamethoxymethyl melamine, and hexamethylol melamine are methoxymethylated or a mixture thereof, hexamethoxyethyl melamine. , Hexaacyloxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof and the like can be mentioned.

Specific examples of the guanamine compound are not particularly limited, but for example, a compound in which 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethylolguanamine are methoxymethylated or a mixture thereof, tetramethoxyethylguanamine. , Tetraacyloxyguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof and the like can be mentioned.

Specific examples of the glycol uryl compound are not particularly limited, but for example, 1 to 4 methylol groups of tetramethylol glycol uryl, tetramethoxyglycol uryl, tetramethoxymethyl glycol uryl, and tetramethylol glycol uryl are methoxymethylated. Examples thereof include a compound or a mixture thereof, a compound in which 1 to 4 methylol groups of tetramethylol glycol uryl are acyloxymethylated, or a mixture thereof.

Specific examples of the urea compound are not particularly limited, but for example, a compound in which 1 to 4 methylol groups of tetramethylol urea, tetramethoxymethylurea, and tetramethylolurea are methoxymethylated or a mixture thereof, tetramethoxyethylurea. And so on.

Further, in the present embodiment, a cross-linking agent having at least one allyl group may be used from the viewpoint of improving the cross-linking property. Specific examples of the cross-linking agent 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) Allylphenols such as hydroxyphenyl) ether, 2,2-bis (3-allyl-4-cyanotophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-cyanophenyl) Propane, bis (3-allyl-4-cyanothyphenyl) sulfone, bis (3-allyl-4-cyanophenyl) sulfide, bis (3-allyl-4-si) Examples thereof include allyl cyanates such as anatophenyl) ether, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropanediallyl ether, pentaerythritol allyl ether, etc., but are limited to those exemplified. It is not something that is done. These may be alone or 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) ) Allylphenols such as propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, and bis (3-allyl-4-hydroxyphenyl) ether are preferable. ..

In the composition for forming an underlayer film for lithography of the present embodiment, the content of the cross-linking agent is not particularly limited, but is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the underlayer film forming material, which is more preferable. Is 10 to 40 parts by mass. By setting the above-mentioned preferable range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect tends to be enhanced, and the film forming property after crosslinking tends to be enhanced.

[Crosslink accelerator]
In the composition for forming a lower layer film for lithography of the present embodiment, a cross-linking accelerator for promoting a cross-linking and curing reaction can be used, if necessary.

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

The cross-linking accelerator includes, but is not limited to, 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylamino). 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 thereof include tetra-substituted phosphonium-tetra-substituted borates such as phosphonium / tetrabutylborate, tetraphenylborone salts such as 2-ethyl-4-methylimidazole / tetraphenylborate, and N-methylmorpholine / tetraphenylborate.

The content of the cross-linking accelerator is usually preferably 0.1 to 10 parts by mass, more preferably controlled, when the total mass of the composition is 100 parts by mass and 100 parts by mass. From the viewpoint of ease and economy, it is 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

[Radical polymerization initiator]
A radical polymerization initiator can be added to the composition for forming an underlayer film for lithography of the present embodiment, if necessary. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or a thermal polymerization initiator that initiates radical polymerization by heat. The radical polymerization initiator may be, for example, at least one selected from the group consisting of a ketone-based photopolymerization initiator, an organic peroxide-based polymerization initiator, and an azo-based polymerization initiator.

The radical polymerization initiator is not particularly limited, and conventionally used ones can be appropriately adopted. For example, 1-hydroxycyclohexylphenylketone, benzyldimethylketal, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2. -Methyl-1-propane-1-one, 2-hydroxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methylpropane-1-one, 2 , 4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide and other ketone photopolymerization initiators, methylethylketone peroxide, cyclohexanone peroxide, methylcyclohexanoneper Oxide, Methylacetate acetate 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) Oxy) -cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) butane, 2,2-bis (4,4-di-t-butylper) Oxycyclohexyl) Propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, t-hexylhydroperoxide, t-butylhydroper 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) hexin-3, isobutylyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoylper Oxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluole benzoyl peroxide, benzoyl peroxide, di-n-propylpa -Oxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3 -Methoxybutyl peroxydicarbonate, di-s-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, Kumilperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate , T-Butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanooate, 2, 5-Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , T-Butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxy-3,5, 5-Trimeter hexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butyl peroxy- m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3', 4,4'-tetra (t-butylper) Examples thereof include organic peroxide-based polymerization initiators such as oxycarbonyl) benzophenone and 2,3-dimethyl-2,3-diphenylbutane.

In addition, 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-Methylpropion amidine) dihydrochloride, 2,2'-azobis (2-methyl-N-phenylpropion amidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropion amidine] Dihydridochloride, 2,2'-azobis [N- (4-hydrophenyl) -2-methylpropion amidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (phenylmethyl) propion amidine] dihydro Chloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propion amidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropion amidine] dihydrochloride , 2,2'-Azobisisobuty [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-diazepine-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (3,3) 4,5,6-Tetrahydropyrimidine-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidine-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-) Il) 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), 4,4'-azobis (4) -Cyanopentanoic acid), 2,2'-azobis [2- (hydroxymethyl) propionitrile] and other azo-based polymerization initiators can also be mentioned. As the radical polymerization initiator used in the present embodiment, one of these may be used alone, two or more thereof may be used in combination, or another known polymerization initiator may be further used in combination. ..

The content of the radical polymerization initiator may be any amount that is stoichiometrically necessary, but when the total mass of the composition containing the above-mentioned compound or resin (component (A)) is 100 parts by mass. It is preferably 0.05 to 25 parts by mass, and more preferably 0.1 to 10 parts by mass. When the content of the radical polymerization initiator is 0.05 parts by mass or more, it tends to be possible to prevent insufficient curing, while the content of the radical polymerization initiator is 25 parts by mass or less. In this case, it tends to be possible to prevent the long-term storage stability of the composition for forming the underlayer film for lithography at room temperature from being impaired.

[Acid generator]
The composition for forming an underlayer film for lithography of the present embodiment may contain an acid generator, if necessary, from the viewpoint of further promoting the cross-linking reaction by heat. As the acid generator, those that generate acid by thermal decomposition, those that generate acid by light irradiation, and the like are known, but any of them can be used.

The acid generator is not particularly limited, but for example, the acid generator described in International Publication No. 2013/024779 can be used. In this embodiment, the acid generator can be used alone or in combination of two or more.

In the composition for forming an underlayer film for lithography of the present embodiment, the content of the acid generator is not particularly limited, but is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the underlayer film forming material. , More preferably 0.5 to 40 parts by mass. By setting the above-mentioned preferable range, the amount of acid generated tends to increase and the crosslinking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.

[Basic compound]
Further, the composition for forming an underlayer film for lithography of the present embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.

The basic compound acts as a quencher for the acid to prevent the acid generated in a smaller amount than the acid generator from advancing the cross-linking reaction. Examples of such basic compounds include primary, secondary or tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, and nitrogen-containing compounds having a carboxy group. Examples thereof include a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative and the like, but the present invention is not particularly limited thereto.

The basic compound used in the present embodiment is not particularly limited, but for example, the compound described in International Publication No. 2013/024779 can be used. In this embodiment, the basic compound may be used alone or in combination of two or more.

In the composition for forming an underlayer film for lithography of the present embodiment, the content of the basic compound is not particularly limited, but is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the underlayer film forming material. , More preferably 0.01 to 1 part by mass. By setting the above-mentioned preferable range, the storage stability tends to be enhanced without excessively impairing the crosslinking reaction.

[Other additives]
Further, the composition for forming an underlayer film for lithography of the present embodiment may contain other resins and / or compounds for the purpose of imparting thermosetting property and controlling the absorbance. Examples of such other resins and / or compounds include naphthalene resin, xylene resin, naphthalene-modified resin, phenol-modified resin of naphthalene resin, polyhydroxystyrene, dicyclopentadiene resin, (meth) acrylate, dimethacrylate, and trimethacrylate. , Tetramethacrylate, vinylnaphthalene, naphthalene rings such as polyacenaphthalene, biphenyl rings such as phenanthrenquinone and fluorene, and resins containing heterocycles such as thiophene and inden and resins not containing aromatic rings; rosin-based. Examples thereof include resins or compounds containing an alicyclic structure such as resins, cyclodextrin, adamantan (poly) all, tricyclodecane (poly) all and derivatives thereof, but the present invention is not particularly limited thereto. Further, the composition for forming an underlayer film for lithography of the present embodiment may contain a known additive. Examples of the known additives include, but are not limited to, ultraviolet absorbers, surfactants, colorants, nonionic surfactants, and the like.

[Method for forming an underlayer film for lithography]
The method for forming a lithographic underlayer film of the present embodiment includes a step of forming an underlayer film on a substrate by using the composition for forming a lithographic underlayer film of the present embodiment.

[Method for forming a resist pattern using a composition for forming an underlayer film for lithography]
The resist pattern forming method using the lithography underlayer film forming composition of the present embodiment is a step of forming an underlayer film on a substrate using the lithography underlayer film forming composition of the present embodiment (A-1). ), A step of forming at least one photoresist layer on the underlayer film (A-2), and a step of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern. (A-3) and.

[Circuit pattern forming method using a composition for forming an underlayer film for lithography]
The circuit pattern forming method using the composition for forming an underlayer film for etching of the present embodiment is a step of forming an underlayer film on a substrate using the composition for forming an underlayer film for etching of the present embodiment (B-1). ), The step of forming an intermediate layer film using a resist intermediate layer film material containing a silicon atom on the lower layer film (B-2), and at least one photoresist layer on the intermediate layer film. (B-3), and after the step (B-3), a predetermined region of the photoresist layer is irradiated with radiation and developed to form a resist pattern (B-4). After the step (B-4), the intermediate layer film is etched using the resist pattern as a mask to form the intermediate layer film pattern (B-5), and the obtained intermediate layer film pattern is etched. A step of etching the lower layer film as a mask to form a lower layer film pattern (B-6) and a step of forming a pattern on the substrate by etching the substrate using the obtained lower layer film pattern as an etching mask (B-6). 7) and.

The method for forming the underlayer film for lithography of the present embodiment is not particularly limited as long as it is formed from the composition for forming the underlayer film for lithography of the present embodiment, and a known method can be applied. For example, the composition for forming an underlayer film for lithography of the present embodiment is applied onto a substrate by a known coating method such as spin coating or screen printing or a printing method, and then removed by volatilizing an organic solvent. , An underlayer film can be formed.

At the time of forming the lower layer film, it is preferable to bake in order to suppress the occurrence of the mixing phenomenon with the upper layer resist and promote the cross-linking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ° C, more preferably 200 to 400 ° C. The baking time is also not particularly limited, but is preferably in the range of 10 to 300 seconds. The thickness of the underlayer film can be appropriately selected according to the required performance and is not particularly limited, but is usually preferably about 30 to 20,000 nm, more preferably 50 to 15,000 nm. Is preferable.

After forming the underlayer film, in the case of a two-layer process, a silicon-containing resist layer is placed on top of it, or in the case of a three-layer process, a silicon-containing intermediate layer is placed on top of it, or a single-layer resist made of ordinary hydrocarbons. It is preferable to prepare a single-layer resist layer containing no silicon. In this case, a known photoresist material can be used to form the resist layer.

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

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

As the silicon-containing intermediate layer for the three-layer process, a polysilsesquioxane-based intermediate layer is preferably used. By giving the intermediate layer an effect as an antireflection film, it tends to be possible to effectively suppress reflection. For example, in the 193 nm exposure process, if a material containing a large amount of aromatic groups and having high substrate etching resistance is used as the underlayer film, the k value tends to be high and the substrate reflection tends to be high, but the reflection is suppressed by the intermediate layer. Therefore, the substrate reflection can be reduced to 0.5% or less. The intermediate layer having such an antireflection effect is not limited to the following, but for 193 nm exposure, a phenyl group or an absorbent group having a silicon-silicon bond is introduced, and the polysilseskioki crosslinked with an acid or heat. Sun is preferably used.

Further, an intermediate layer formed by the Chemical Vapor Deposition (CVD) method can also be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, and for example, a SiON film is known. In general, the formation of an intermediate layer by a wet process such as a spin coating method or screen printing is simpler and more cost effective than the CVD method. The upper layer resist in the three-layer process may be either a positive type or a negative type, and the same single-layer resist as normally used can be used.

Further, the underlayer film in the present 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 underlayer film of the present embodiment has excellent etching resistance for base processing, it can be expected to function as a hard mask for base processing.

When the resist layer is formed from the photoresist material, a wet process such as a spin coating method or screen printing is preferably used as in the case of forming the underlayer film. Further, after applying the resist material by a spin coating method or the like, prebaking is usually performed, and this prebaking is preferably performed at 80 to 180 ° C. for 10 to 300 seconds. After that, a resist pattern can be obtained by performing exposure, post-exposure baking (PEB), and development according to a conventional method. 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 according to the photoresist material to be used. In general, high-energy rays having a wavelength of 300 nm or less, specifically, excimer lasers having a wavelength of 248 nm, 193 nm, and 157 nm, soft X-rays having a wavelength of 3 to 20 nm, electron beams, X-rays, and the like can be mentioned.

The resist pattern formed by the above method has the pattern collapse suppressed by the underlayer film in the present embodiment. Therefore, by using the underlayer film in the present embodiment, a finer pattern can be obtained, and the exposure amount required 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 as the etching of the lower layer film in the two-layer process. As the gas etching, etching using oxygen gas is preferable. In addition to oxygen gas, it is also possible to add an inert gas such as He or Ar, or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO _{2, or} H ₂ gas. It is also possible to perform gas etching using only CO, CO ₂ , NH ₃ , N ₂ , NO _{2, and} H ₂ gases without using oxygen gas. In particular, the latter gas is preferably used to protect the side wall to prevent undercutting of the side wall of the pattern.

On the other hand, gas etching is also preferably used in the etching of the intermediate layer in the three-layer process. As the gas etching, the same ones as described in the above two-layer process can be applied. In particular, the processing of the intermediate layer in the three-layer process is preferably performed by using a fluorocarbon-based gas and using the resist pattern as a mask. After that, the lower layer film can be processed by, for example, performing oxygen gas etching using the intermediate layer pattern as a mask as described above.

Here, when an inorganic hard mask intermediate layer film is formed as an intermediate layer, a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film (SiON film) are formed by a CVD method, an atomic layer deposition (ALD) method, or the like. To. The method for forming the nitride film is not limited to the following, and for example, the methods described in JP-A-2002-334869 (Patent Document 4) and International Publication No. 2004/06637 (Patent Document 5) can be used. can. A photoresist film can be formed directly on such an intermediate layer film, but an organic antireflection film (BARC) is formed on the intermediate layer film by spin coating, and a photoresist film is formed on the organic antireflection film (BARC). You may.

As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. By giving the resist intermediate layer film an effect as an antireflection film, it tends to be possible to effectively suppress reflection. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, and are, for example, in JP-A-2007-226170 (Patent Document 6) and JP-A-2007-226204 (Patent Document 7). The ones described can be used.

Further, the next etching of the substrate can also be performed by a conventional method. For example, if the substrate is SiO ₂ or SiN, the etching is mainly composed of fluorogas, and if the substrate is p—Si, Al, or W, chlorine-based or bromine-based etching is performed. Etching mainly composed of gas can be performed. When the substrate is etched with a freon 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 a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled off, and generally, dry etching peeling is performed with a freon-based gas after the substrate is processed. ..

The underlayer film in the present embodiment is characterized by having excellent etching resistance of these substrates. As the substrate, a known substrate can be appropriately selected and used, and examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. .. Further, the substrate may be a laminated body having a film to be processed (substrate to be processed) on a base material (support). Such processed films 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 stopper films thereof. Etc., and usually, a material different from the base material (support) is used. The thickness of the substrate or the film to be processed is not particularly limited, but is usually preferably about 50 to 1,000,000 nm, and more preferably 75 to 500,000 nm.

[Permanent resist film]
In addition, the resist permanent film formed by applying the composition, which can also produce a resist permanent film using the composition, is a permanent film that remains in the final product after forming a resist pattern as needed. It is suitable as. Specific examples of the permanent film are not particularly limited, but for example, in the case of semiconductor devices, a package adhesive layer such as a solder resist, a package material, an underfill material, and a circuit element, an adhesive layer between an integrated circuit element and a circuit board, and a thin display. Related examples include a thin film protective film, a liquid crystal color filter protective film, a black matrix, and a spacer. In particular, the permanent film made of the above composition has an extremely excellent advantage that it is excellent in heat resistance and moisture resistance and is less contaminated by sublimation components. In particular, in the display material, it is a material having high sensitivity, high heat resistance, and moisture absorption reliability with little deterioration of image quality due to important contamination.

When the composition is used for a permanent resist film, in addition to a curing agent, various additives such as other resins, surfactants and dyes, fillers, cross-linking agents, and dissolution accelerators are added as necessary. By dissolving in an organic solvent, a composition for a permanent resist film can be obtained.

The lithography film forming composition and the resist permanent film composition can be adjusted by blending the above components and mixing them using a stirrer or the like. When the resist underlayer film composition or the resist permanent film composition contains a filler or a pigment, it should be dispersed or mixed using a disperser such as a dissolver, a homogenizer, or a three-roll mill. Can be done.
[Method for purifying compounds and / or resins]
The method for purifying the compound and / or the resin of the present embodiment is a step of dissolving the compound of the present embodiment and / or the resin of the present embodiment in a solvent to obtain a solution (S), and the obtained solution (S). An organic solvent that is immiscible with water as a solvent used in the step of obtaining the solution (S), which comprises a first extraction step of extracting impurities in the compound and / or the resin by contacting an acidic aqueous solution with the compound. including.

In the first extraction step, the resin is preferably a resin obtained by reacting the compound represented by the above formula (A) with a compound having a cross-linking reactivity. According to the purification method of the present embodiment, the content of various metals that can be contained as impurities in the compound or resin having the above-mentioned specific structure can be reduced.

More specifically, in the purification method of the present embodiment, the above compound and / or the above resin is dissolved in an organic solvent immiscible with water to obtain a solution (S), and the solution (S) is further used as an acidic aqueous solution. The extraction process can be performed by contacting with. As a result, the metal content contained in the solution (S) containing the compound and / or the resin of the present embodiment was transferred to the aqueous phase, and then the organic phase and the aqueous phase were separated to reduce the metal content. The compound and / or resin of the present embodiment can be obtained.

The compound and / or resin of the present embodiment used in the purification method of the present embodiment may be used alone, but two or more kinds may be mixed. Further, the compound and / or the resin of the present embodiment may contain various surfactants, various cross-linking agents, various acid generators, various stabilizers and the like.

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

Specific examples of the solvent immiscible with water are not limited to the following, but for example, 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 ketone, Ketones such as 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 ether acetate Glycol ether acetates such as; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and chloroform. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, and methyl isobutyl ketone, ethyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate are more preferable. Methyl isobutyl ketone and ethyl acetate are even more preferable. Methyl isobutyl ketone, ethyl acetate, etc. have a relatively high saturated solubility and a relatively low boiling point of the compound and the resin of the present embodiment, and thus have a load in the step of industrially distilling off the solvent or removing it by drying. Can be reduced. Each of these solvents can be used alone, or two or more of them can be mixed and used.

The acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, and examples thereof include a mineral acid aqueous solution in which an inorganic compound is dissolved in water and an organic acid aqueous solution in which an organic compound is dissolved in water. Be done. The mineral acid aqueous solution is not particularly limited, and examples thereof include a mineral acid aqueous solution in which one or more kinds of mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are dissolved in water. The organic acid aqueous solution is not particularly limited, but for example, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartrate acid, citric acid, methanesulfonic acid, phenolsulfonic acid, and p-toluene. Examples thereof include an organic acid aqueous solution in which one or more kinds of organic acids such as sulfonic 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 one or more organic acid aqueous solutions selected from the group consisting of tartrate acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid, preferably sulfuric acid, nitric acid, acetic acid and oxalic acid. An aqueous solution of a carboxylic acid such as tartaric acid or citric acid is more preferable, an aqueous solution of sulfuric acid, oxalic acid, tartaric acid or citric acid is more preferable, and an aqueous solution of oxalic acid is even more preferable. It is considered that polyvalent carboxylic acids such as oxalic acid, tartaric acid, and citric acid are coordinated to metal ions and have a chelating effect, so that the metal can be removed more effectively. Further, as the water used here, it is preferable to use water having a low metal content, for example, ion-exchanged water, etc., in line with the purpose of the purification method of the present embodiment.

The pH of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the compound and / or the resin of the present embodiment. Usually, the pH range is about 0 to 5, preferably about 0 to 3.

The amount of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, but the present invention is concerned from the viewpoint of reducing the number of extractions for removing metals and ensuring operability in consideration of the total amount of liquid. It is preferable to adjust the amount used. 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, the solution is brought into contact with the acidic aqueous solution as described above, the compound and / or the resin of the present embodiment, and the solution (S) containing a solvent immiscible with water. A metal component can be extracted from the compound or the resin in (S).

In the purification method of the present embodiment, it is preferable that the solution (S) further contains an organic solvent miscible with water. When an organic solvent miscible with water is contained, the amount of the compound and / or resin of the present embodiment to be charged can be increased, the liquid separation property is improved, and purification can be performed with high pot efficiency. be. The method of adding an organic solvent that is miscible with water is not particularly limited. For example, any of a method of adding to a solution containing an organic solvent in advance, a method of adding to water or an acidic aqueous solution in advance, and a method of adding after contacting a solution containing an organic solvent with water or an acidic aqueous solution may be used. Among these, the method of adding to a solution containing an organic solvent in advance is preferable in terms of workability of operation and ease of control of the amount to be charged.

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

Specific examples of the organic solvent to be mixed with water used in the purification method of the present embodiment are not limited to the following, but are not limited to, for example, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol and isopropanol. Classes; 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 preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable. Each of these solvents can be used alone, or two or more of them can be mixed and used.

The temperature at which the extraction process is performed is usually 20 to 90 ° C, preferably 30 to 80 ° C. The extraction operation is performed by, for example, stirring well and then allowing the mixture to stand still. As a result, the metal content contained in the solution containing the compound and / or the resin and the organic solvent of the present embodiment is transferred to the aqueous phase. Further, by this operation, the acidity of the solution is lowered, and the deterioration of the compound and / or the resin of the present embodiment can be suppressed.

Since the mixed solution is separated into a solution phase containing the compound and / or the resin and the solvent of the present embodiment by standing still, and an aqueous phase, the compound and / or the resin and the solvent of the present embodiment are separated by decantation or the like. Recover the containing solution phase. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation between the solution phase containing the solvent and the aqueous phase. Usually, the standing time is 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more. Further, the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of 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). ) Is preferably included. Specifically, for example, after performing the above extraction treatment using an acidic aqueous solution, the solution phase containing the compound and / or resin and solvent of the present embodiment extracted and recovered from the aqueous solution is further added with water. It is preferable to use it for extraction treatment. The above-mentioned extraction treatment with water is not particularly limited, but can be carried out, for example, by mixing the above-mentioned solution phase and water well by stirring or the like, and then allowing the obtained mixed solution to stand still. The mixed solution after standing is separated into a solution phase containing the compound and / or the resin and the solvent of the present embodiment and an aqueous phase, so that the compound and / or the resin and the solvent of the present embodiment are separated by decantation or the like. The solution phase containing the above can be recovered.

Further, the water used here is preferably water having a low metal content, for example, ion-exchanged water, for the purpose of the present embodiment. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times. Further, the conditions such as the ratio of use of both in the extraction treatment, the temperature, and the time are not particularly limited, but the same as in the case of the contact treatment with the acidic aqueous solution described above may be used.

Moisture that can be mixed in the solution containing the compound and / or the resin and the solvent of the present embodiment 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 the resin of the present embodiment to an arbitrary concentration.

The method for isolating the compound and / or the resin of the present embodiment from the obtained solution containing the compound and / or the resin of the present embodiment is not particularly limited, and is removed under reduced pressure, separated by reprecipitation, and It can be carried out by a known method such as a combination thereof. If necessary, known treatments such as concentration operation, filtration operation, centrifugation operation, and drying operation can be performed.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, this embodiment is not particularly limited to these examples.

The method for analyzing and evaluating the compound is as follows.
<Molecular weight>
The molecular weight of the compound was measured by LC-MS analysis using an Accuracy UPLC / MALDI-Snapt HDMS manufactured by Water.
<Measurement of pyrolysis temperature>
Using an EXSTAR6000DSC device manufactured by SII Nanotechnology, about 5 mg of a sample was placed in an aluminum unsealed container, and the temperature was raised to 500 ° C. at a heating rate of 10 ° C./min in a nitrogen gas (30 ml / min) stream. At that time, the temperature at which the reduced portion appears at the baseline was defined as the thermal decomposition temperature.

<Test method for heat resistance>
Using an EXSTAR6000DSC device manufactured by SII Nanotechnology, about 5 mg of a sample was placed in an aluminum unsealed container, and the temperature was raised to 500 ° C. at a heating rate of 10 ° C./min in a nitrogen gas (30 ml / min) stream. At that time, the temperature at which the reduced portion appeared at the baseline was defined as the thermal decomposition temperature (Tg), and the heat resistance was evaluated according to the following criteria.
Evaluation A: Pyrolysis temperature is ≧ 150 ℃
Evaluation C: Pyrolysis temperature is <150 ° C

<Solubility>
The amount of the compound dissolved in propylene glycol monomethyl ether (PGME) at 23 ° C. was evaluated according to the following criteria.
Evaluation A: 10% by mass or more Evaluation C: Less than 10% by mass

(Synthesis Example 1) Synthesis of BisN-1 A container having an internal volume of 100 ml equipped with a stirrer, a cooling tube and a burette was prepared. In this container, 1.52 g (9.5 mmol) of 2,7-dihydroxynaphthalene (reagent manufactured by Sigma-Aldrich) and 0.56 g (4.7 mmol) of 4-methylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Company), 1 , 4-Dioxane (30 ml) was charged, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid was added to prepare a reaction solution. The reaction was carried out by stirring the reaction solution at 90 ° C. for 3.5 hours. Next, the reaction solution was cooled to 40 ° C., 10 ml of hexane was added dropwise, the mixture was cooled to 10 ° C. to precipitate the reaction product, filtered, washed with hexane, and then separated and purified by column chromatography. 0.5 g of the target compound (BisN-1) represented by the following formula was obtained.
The following peaks were found by 400 MHz- ^{1 1} H-NMR, and it was confirmed that the chemical structure had the following formula.
^{1 1} H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.2 (2H, O—H), 6.8 to 7.8 (14H, Ph-H), 5.3 (1H, CH) 2.2 (3H, Ph-CH ₃ ) )
The molecular weight of the obtained compound was measured by the above method and found to be 404.

(Synthesis Example 2 to Synthesis Example 12) 2,7-Dihydroxynaphthalene and 4-methylbenzaldehyde, which are raw materials for the synthesis of BisN-2 to BisN-12, are changed as shown in Table 1, and the others are the same as those of Synthesis Example 1. The same procedure was carried out to obtain the target products BisN-2 to BisN-12.
Each compound was identified by ¹ H-NMR and molecular weight. The results are shown in Table 2.

(Synthesis Example 13) Synthesis of resin (R1-BisN-1) A four-necked flask having a bottom-pullable internal volume of 1 L equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. In this four-necked flask, 28.4 g (70 mmol, manufactured by Mitsubishi Gas Chemical Company, Inc.) of the compound (BisN-1) obtained in Synthesis Example 1 and 21.0 g of a 40 mass% formaldehyde aqueous solution (21.0 g) in a nitrogen stream. 280 mmol of formaldehyde (manufactured by Mitsubishi Gas Chemical Company, Inc.) and 0.97 mL of 98 mass% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted under normal pressure at 100 ° C. for 7 hours. Then, 180.0 g of orthoxylen (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution as a diluting solvent, and after standing, the aqueous phase of the lower phase was removed. Further, the mixture was neutralized and washed with water, and orthoxylene was distilled off under reduced pressure to obtain 30.7 g of a brown solid resin (R1-BisN-1).

The obtained resin (R1-BisN-1) was Mn: 1972, Mw: 3710, and Mw / Mn: 1.88.

(Synthesis Example 14) Synthesis of resin (R2-BisN-1) A four-necked flask having a bottom-pullable internal volume of 1 L equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. In this four-necked flask, 28.4 g (70 mmol, manufactured by Mitsubishi Gas Chemical Company, Inc.) and 50.9 g (280 mmol) of the compound (BisN-1) obtained in Synthesis Example 1 in a nitrogen stream. , Mitsubishi Gas Chemical Co., Ltd.), Anisol (manufactured by Kanto Chemical Co., Ltd.) 100 mL and oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) 10 mL, and under normal pressure, recirculate at 100 ° C for 7 hours. It was reacted. Then, 180.0 g of orthoxylen (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution as a diluting solvent, and after standing, the aqueous phase of the lower phase was removed. Further, the mixture was neutralized and washed with water, and the solvent of the organic phase and the unreacted 4-biphenylaldehyde were distilled off under reduced pressure to obtain 38.5 g of a brown solid resin (R2-BisN-1).

The obtained resin (R2-BisN-1) had Mn: 1520, Mw: 2453, and Mw / Mn: 1.61.

(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 this four-necked flask, 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Company, Inc.) and 2.1 kg of 40 mass% formalin aqueous solution (28 mol as formaldehyde, Mitsubishi Gas Chemical Company, Inc.) in a nitrogen stream. ) And 98% by mass sulfuric acid (manufactured by Kanto Kagaku Co., Ltd.) were charged and reacted for 7 hours under normal pressure while refluxing at 100 ° C. Then, 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, the aqueous phase of the lower 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 a light brown solid dimethylnaphthalene formaldehyde resin.

Subsequently, a four-necked flask having an internal volume of 0.5 L equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. In this four-necked flask, 100 g (0.51 mol) of dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of p-toluenesulfonic acid were charged under a nitrogen stream, and the temperature was raised to 190 ° C. 2 After heating for hours, the mixture was stirred. After that, 52.0 g (0.36 mol) of 1-naphthol was further added, the temperature was further raised to 220 ° C., and the reaction was carried out 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 dark brown solid modified resin (CR-1).

[Examples 1 to 12]
Table 3 shows the results of evaluation of the solubility in propylene glycol monomethyl ether (PGME) using BisN-1 to BisN-12, R1-BisN-1, and R2-BisN-1.

表３から明らかなように、実施例１～実施例１４で用いた化合物は、溶媒への溶解性に優れることが確認できた。

As is clear from Table 3, it was confirmed that the compounds used in Examples 1 to 14 were excellent in solubility in the solvent.

[Examples 15 to 26, Comparative Example 1]
(Heat resistance and resist performance)
Table 4 shows the results of heat resistance test and resist performance evaluation using BisN-1 to BisN-12 and CR-1.

(Preparation of resist composition)
Using each of the compounds synthesized above, a resist composition was prepared according to the formulation shown in Table 4. Among the components of the resist composition in Table 4, the following were used as the acid generator (C), the acid diffusion control agent (E), and the solvent.
Acid generator (C)
P-1: Triphenylbenzene Sulfonium Trifluoromethanesulfonate (Midori Kagaku Co., Ltd.)
Acid diffusion control agent (E)
Q-1: Trioctylamine (Tokyo Chemical Industry Co., Ltd.)
Solvent S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

(Method for evaluating resist performance of resist composition)
A uniform resist composition was spin-coated on a clean silicon wafer and then pre-exposed baked (PB) 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 having a 1: 1 line and space setting at 50 nm intervals using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Inc.). After the irradiation, each resist film was heated at a predetermined temperature for 90 seconds and immersed in TMAH 2.38 mass% alkaline developer for 60 seconds for development. Then, the resist film was washed with ultrapure water for 30 seconds and dried to form a positive resist pattern. The line and space of the formed resist pattern was observed with a scanning electron microscope (S-4800 manufactured by Hitachi High Technology Co., Ltd.), and the reactivity of the resist composition by electron beam irradiation was evaluated.

As is clear from Table 4, it was confirmed that the compounds used in Examples 15 to 26 had good heat resistance, but the compounds used in Comparative Example 1 had inferior heat resistance.

Regarding the resist pattern evaluation, in Examples 15 to 26, a good resist pattern was obtained by irradiating with an electron beam having a 1: 1 line and space setting at intervals of 50 nm. On the other hand, in Comparative Example 1, a good resist pattern could not be obtained.

As described above, the compound satisfying the requirements of the present invention has higher heat resistance than the comparative compound (CR-1) and can impart a good resist pattern shape. As long as the above-mentioned requirements of the present invention are satisfied, the same effect is exhibited with compounds other than the compounds described in Examples.

[Examples 27 to 38, Comparative Example 2]
(Preparation of radiation-sensitive composition)
The components shown in Table 5 were mixed to prepare a uniform solution, and then the obtained uniform solution was filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.1 μm to prepare a radiation-sensitive composition. The following evaluations were made for each of the prepared radiation-sensitive compositions.

The following resist material was used as the resist base material in Comparative Example 2.
PHS-1: Polyhydroxystyrene Mw = 8000 (Sigma-Aldrich)
The following was used as the photoactive compound (B).
B-1: Naftquinone diazide-based photosensitive agent of the following chemical structural formula (G) (4NT-300, Toyo Gosei Co., Ltd.)
The following solvents were used as the solvent.
S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

(Evaluation of resist performance of radiation-sensitive composition)
The radiation-sensitive composition obtained above was rotationally coated on a clean silicon wafer and then pre-exposed baked (PB) in an oven at 110 ° C. to form a resist film having a thickness of 200 nm. The resist film was exposed to ultraviolet rays using an ultraviolet exposure device (Mask Aligner MA-10 manufactured by Mikasa). As the ultraviolet lamp, an ultrahigh pressure mercury lamp (relative intensity ratio is g line: h line: i line: j line = 100: 80: 90: 60) was used. After irradiation, the resist film was heated at 110 ° C. for 90 seconds and immersed in TMAH 2.38 mass% alkaline developer for 60 seconds for development. Then, the resist film was washed with ultrapure water for 30 seconds and dried to form a 5 μm positive resist pattern.

In the formed resist pattern, the obtained line and space was observed with a scanning electron microscope (S-4800 manufactured by Hitachi High-Technology Co., Ltd.). The line edge roughness was good when the unevenness of the pattern was less than 50 nm.

When the radiation-sensitive compositions of Examples 27 to 38 were used, a good resist pattern having a resolution of 5 μm could be obtained. In addition, the roughness of the pattern was small and good.

On the other hand, when the radiation-sensitive composition in Comparative Example 2 was used, a good resist pattern having a resolution of 5 μm could be obtained. However, the roughness of the pattern was large and poor.

As described above, the radiation-sensitive compositions of Examples 27 to 38 can form a resist pattern having a smaller roughness and a better shape than the radiation-sensitive compositions of Comparative Example 2. I understand. As long as the above-mentioned requirements of the present invention are satisfied, radiation-sensitive compositions other than those described in Examples show the same effect.

The compounds obtained in Synthesis Examples 1 to 12 have a relatively low molecular weight and a low viscosity, and the glass transition temperature is as low as 150 ° C. or lower, so that a lower layer for lithography using the compounds is used. The film-forming material can relatively advantageously enhance the embedding properties and the flatness of the film surface. Further, since the pyrolysis temperature is 150 ° C. or higher (evaluation A) and has high heat resistance, it can be used even under high temperature baking conditions.

[Examples 39 to 52, Comparative Example 3]
(Preparation of composition for forming underlayer film for lithography)
A composition for forming an underlayer film for lithography was prepared so as to have the compositions shown in Tables 6-1 and 6-2. Next, these composition for forming a lower layer film for lithography was rotationally applied onto a silicon substrate, and then baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to prepare a lower layer film having a film thickness of 200 nm. .. The following were used as the acid generator, the cross-linking agent and the organic solvent.
Acid generator: Midori Kagaku Co., Ltd. Jitterly Butyl Diphenyliodonium Nonafluoromethane Sulfonate (DTDPI)
Crosslinking agent: Nikalac MX270 manufactured by Sanwa Chemical Co., Ltd.
Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA)
Novolac: PSM4357 manufactured by Gun Ei Chemical Industry Co., Ltd.

Next, an etching test was performed under the conditions shown below to evaluate the etching resistance. The evaluation results are shown in Tables 6-1 and 6-2.

[Etching test]
Etching device: RIE-10NR manufactured by SAMCO International Corporation
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)

(Evaluation of etching resistance)
The etching resistance was evaluated by the following procedure. First, a novolak underlayer film was prepared under the above conditions except that novolak (PSM4357 manufactured by Gun Ei Chemical Industry Co., Ltd.) was used. Then, the above etching test was performed on the underlayer film of this novolak, and the etching rate at that time was measured.

Next, the lower layer films of Examples 39 to 52, Examples 39A to 52A, and Comparative Example 3 were prepared under the same conditions as the lower layer film of Novolac, and the above etching test was performed in the same manner. The etching rate was measured.

Then, the etching resistance was evaluated according to the following evaluation criteria based on the etching rate of the underlayer film of novolak.
[Evaluation criteria]
A: Etching rate is less than -10% compared to Novolac underlayer B: Etching rate is -10% to + 5% compared to Novolac underlayer.
C: Etching rate is over + 5% compared to the underlayer film of Novolac

It was found that in Examples 39 to 52 and 39A to 52A, an excellent etching rate was exhibited as compared with the underlayer film of Novolac. On the other hand, in Comparative Example 3, it was found that the etching rate was inferior to that of the underlayer film of Novolac.

[Examples 53 to 66, Examples 53A to 66A, Comparative Example 4]
Next, the composition for forming an underlayer film for lithography used in Examples 39 to 52 and 39A to 52A was applied onto a 60 nm line-and-space SiO ₂ substrate having a film thickness of 80 nm and having a temperature of 240 ° C. A 90 nm underlayer film was formed by baking for 60 seconds.

(Evaluation of embedding property)
The embedding property was evaluated by the following procedure. A cross section of the membrane obtained under the above conditions was cut out and observed with an electron beam microscope to evaluate the implantability. The evaluation results are shown in Tables 7-1 and 7-2.

[Evaluation criteria]
A: The underlayer film is embedded in the uneven portion of the SiO ₂ substrate of 60 nm line and space without any defect.
C: There is a defect in the uneven portion of the SiO ₂ substrate of 60 nm line and space, and the underlayer film is not embedded.

It was found that the implantability was good in Examples 53 to 66 and 53A to 66A. On the other hand, in Comparative Example 4, it was found that a defect was found in the uneven portion of the SiO ₂ substrate and the embedding property was inferior.

[Example 67]
Next, the composition for forming an underlayer film for lithography used in Example 39 was applied onto a SiO ₂ substrate having a film thickness of 300 nm, and baked at 240 ° C. for 60 seconds and then at 400 ° C. for 120 seconds to obtain a film thickness. An 85 nm underlayer film was formed. A resist solution for ArF was applied onto this lower film and baked at 130 ° C. for 60 seconds to form a photoresist layer having a film thickness of 140 nm.

The ArF resist solution contains 5 parts by mass of the compound of the following formula (16), 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.

（式（１６）中、４０、４０、２０とあるのは、各構成単位の比率を示すものであり、ブロック共重合体を示すものではない。）The compound of the following formula (16) was prepared as follows. That is, 2-methyl-2-methacryloyloxyadamantane 4.15 g, methacrylloyloxy-γ-butyrolactone 3.00 g, 3-hydroxy-1-adamantyl methacrylate 2.08 g, azobisisobutyronitrile 0.38 g, and tetrahydrofuran. It was dissolved in 80 mL to prepare a reaction solution. The reaction solution was polymerized under a nitrogen atmosphere at a reaction temperature of 63 ° C. for 22 hours, and then the reaction solution was added dropwise to 400 mL of n-hexane. The produced resin thus obtained was coagulated and purified, the produced white powder was filtered, and dried at 40 ° C. under reduced pressure overnight to obtain a compound represented by the following formula (16).

(In the formula (16), 40, 40, and 20 indicate the ratio of each structural unit, not the block copolymer.)

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

[Comparative Example 5]
A photoresist layer was directly formed on the SiO ₂ substrate in the same manner as in Example 67 except that the underlayer film was not formed, and a positive resist pattern was obtained.

[evaluation]
For each of Example 67 and Comparative Example 5, the shapes of the obtained resist patterns of 45 nm L / S (1: 1) and 80 nm L / S (1: 1) were measured by an electron microscope (S-4800) manufactured by Hitachi, Ltd. Was observed using. Regarding the shape of the resist pattern after development, those having no pattern collapse and having good rectangularity were evaluated as good, and those not having good rectangularness were evaluated as defective. In addition, as a result of the 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 that can draw a good pattern shape was used as the sensitivity and used as an evaluation index. The results are shown in Table 8.

As is clear from Table 8, it was confirmed that the resist pattern in Example 67 was significantly superior in resolution and sensitivity as compared with Comparative Example 5. In addition, it was confirmed that the resist pattern shape after development did not collapse and the rectangularity was good. Further, from the difference in the resist pattern shape after development, it was shown that the underlayer film forming material for lithography in Example 67 has good adhesion to the resist material.

[Example 68]
The composition for forming a lower layer film for lithography used in Example 39 was applied onto a SiO ₂ substrate having a film thickness of 300 nm, and baked at 240 ° C. for 60 seconds and then at 400 ° C. for 120 seconds to form a lower layer having a film thickness of 90 nm. A film was formed. A silicon-containing intermediate layer material was applied onto the lower layer film and baked at 200 ° C. for 60 seconds to form an intermediate layer film having a film thickness of 35 nm. Further, the resist solution for ArF was applied onto the intermediate layer film and baked at 130 ° C. for 60 seconds to form a photoresist layer having a film thickness of 150 nm. As the silicon-containing intermediate layer material, the silicon atom-containing polymer described in JP-A-2007-226170 <Synthesis Example 1> was used.

Next, the photoresist layer was mask-exposed using an electron beam lithography system (ELS-7500, 50 keV) and baked (PEB) at 115 ° C. for 90 seconds to obtain 2.38 mass% tetramethylammonium hydroxide. By developing with an aqueous solution of (TMAH) for 60 seconds, a positive resist pattern of 45 nm L / S (1: 1) was obtained.

Then, using RIE-10NR manufactured by Samco International Co., Ltd., the silicon-containing intermediate layer film (SOG) is dry-etched using the obtained resist pattern as a mask, and then the obtained silicon-containing intermediate layer film pattern is obtained. The dry etching process of the lower layer film used as a mask and the dry etching process 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 interlayer film
Output: 50W
Pressure: 20Pa
Time: 1 min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 8: 2 (sccm)
Etching conditions for resist interlayer film of resist interlayer film
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 the resist underlayer film pattern on the SiO ₂ film
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: C ₅ F ₁₂ gas flow rate: C ₂ F ₆ gas flow rate: O ₂ gas flow rate
= 50: 4: 3: 1 (sccm)

[evaluation]
When the pattern cross section (shape of the SiO ₂ film after etching) of Example 68 obtained as described above was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., the lower layer of the present invention was observed. In the example using the film, it was confirmed that the shape of the SiO ₂ film after etching in the multilayer resist processing was rectangular, and no defects were observed, which was good.

The present invention is a compound that can be used as a component of a photoresist, a resin raw material for a material for electric / electronic parts, a curable resin raw material such as a photocurable resin, a resin raw material for a structural material, a resin curing agent, or the like. , Has industrial availability.

Claims (23)

A resist composition containing a compound represented by the following formula (2).

(In the formula (2), R ^3B is a linear or branched alkyl group having 1 to 30 carbon atoms which may independently have a substituent, and m ^6B is 1 to 5 Is an integer of.) The resist composition according to claim 1, wherein the compound represented by the formula (2) is a compound selected from the group represented by the following formulas (2-1) to (2-12).

A resist composition containing a resin having a structural unit derived from the compound according to claim 1 or 2. The resist composition according to any one of claims 1 to 3, further comprising a solvent. The resist composition according to any one of claims 1 to 4, further comprising an acid generator. The resist composition according to any one of claims 1 to 5, further comprising an acid diffusion control agent. A step of forming a resist film on a substrate by using the resist composition according to any one of claims 1 to 6.
A step of exposing at least a part of the formed resist film, and
A resist pattern forming method comprising a step of developing the exposed resist film to form a resist pattern. It contains one or more components (A) selected from the group consisting of the compound according to claim 1 or 2 and the resin according to claim 3, a diazonaphthoquinone photoactive compound (B), and a solvent. In the radiation-sensitive composition, the content of the solvent is 20 to 99% by mass with respect to 100% by mass of the total amount of the radiation-sensitive composition, and the content of components other than the solvent is the feeling. A radiation-sensitive composition which is 1 to 80% by mass with respect to 100% by mass of the total amount of the radioactive composition. The content ratio ((A) / (B) of the component (A), the diazonaphthoquinone photoactive compound (B), and any other optional component (D) that may be optionally contained in the radiation-sensitive composition. ) / (D)) is 1 to 99% by mass / 99 to 1% by mass / 0 to 98% by mass with respect to 100% by mass of the solid content of the radiation-sensitive composition, according to claim 8. Radiation sensitive composition. The radiation-sensitive composition according to claim 8 or 9, wherein an amorphous film can be formed by spin coating. A method for producing an amorphous film, which comprises a step of forming an amorphous film on a substrate by using the radiation-sensitive composition according to any one of claims 8 to 10. A step of forming a resist film on a substrate using the radiation-sensitive composition according to any one of claims 8 to 10, a step of exposing at least a part of the formed resist film, and an exposure. A method for forming a resist pattern, which comprises a step of developing the resist film to form a resist pattern. An underlayer film forming material for lithography containing at least one selected from the group consisting of the compound according to claim 1 or 2 and the resin according to claim 3. A composition for forming an underlayer film for lithography, which comprises the material for forming an underlayer film for lithography according to claim 13 and a solvent. The composition for forming an underlayer film for lithography according to claim 14, further comprising an acid generator. The composition for forming an underlayer film for lithography according to claim 14 or 15, further comprising a cross-linking agent. A method for producing an underlayer film for lithography, which comprises a step of forming an underlayer film on a substrate by using the composition for forming an underlayer film for lithography according to any one of claims 14 to 16. A step of forming an underlayer film on a substrate by using the composition for forming an underlayer film for lithography according to any one of claims 14 to 16.
A step of forming at least one photoresist layer on the underlayer film, and
A resist pattern forming method comprising a step of irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist pattern to form a resist pattern. A step of forming an underlayer film on a substrate by using the composition for forming an underlayer film for lithography according to any one of claims 14 to 16.
A step of forming an intermediate layer film on the lower layer film using a resist intermediate layer film material containing a silicon atom, and a step of forming the intermediate layer film.
A step of forming at least one photoresist layer on the intermediate layer film and
A step of irradiating a predetermined area of the photoresist layer with radiation and developing the resist layer to form a resist pattern.
A step of etching the intermediate layer film using the resist pattern as a mask to form an intermediate layer film pattern,
A step of etching the lower layer film using the intermediate layer film pattern as an etching mask to form a lower layer film pattern, and a step of forming the lower layer film pattern.
A circuit pattern forming method comprising a step of etching a substrate using the underlayer film pattern as an etching mask to form a pattern on the substrate. A step of dissolving one or more selected from the group consisting of the compound according to claim 1 or 2 and the resin according to claim 3 in a solvent to obtain a solution (S), and the obtained solution (S). The solvent used in the step of obtaining the solution (S) includes a solvent immiscible with water, which comprises a first extraction step of extracting impurities in the compound and / or the resin by contacting with an acidic aqueous solution. , The method for purifying the compound and the resin. The acidic aqueous solution is a mineral acid aqueous solution or an organic acid aqueous solution, and the mineral acid aqueous solution is a mineral acid aqueous solution in which one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid is dissolved in water. The organic acid aqueous solution comprises acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid. The purification method according to claim 20, which is an organic acid aqueous solution in which one or more selected from the group is dissolved in water. The solvent immiscible with water is one or more solvents selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate, claim 20 or the like. 21. The purification method according to 21. 20 to claim 20, wherein after the first extraction step, the solution phase containing the compound and / or the resin is further brought into contact with water to extract impurities in the compound and / or the resin. The purification method according to any one of 22.