KR20190049731A - COMPOUND, RESIN, COMPOSITION, AND RESIST PATTERN FORMING METHOD - Google Patents

Abstract

(식(0) 중, R^Y는, 수소원자이며, R^Z는, 탄소수 1~60의 N가의 기 또는 단결합이며, R^T는, 각각 독립적으로, 치환기를 가질 수도 있는 탄소수 1~30의 알킬기, 치환기를 가질 수도 있는 탄소수 6~30의 아릴기, 치환기를 가질 수도 있는 탄소수 2~30의 알케닐기, 치환기를 가질 수도 있는 탄소수 1~30의 알콕시기, 할로겐원자, 니트로기, 아미노기, 카르본산기, 티올기 또는 수산기이며, 상기 알킬기, 상기 아릴기, 상기 알케닐기 및 상기 알콕시기는, 에테르결합, 케톤결합 또는 에스테르결합을 포함하고 있을 수도 있고, 여기서, R^T의 적어도 1개는 수산기이며, 또한 R^T의 적어도 1개는 탄소수 2~30의 알케닐기이며, X는, 산소원자, 황원자, 단결합 또는 무가교인 것을 나타내고, m은, 각각 독립적으로 0~9의 정수이며, 여기서, m의 적어도 1개는 2~9의 정수 또는 m의 적어도 2개는 1~9의 정수이며, N은, 1~4의 정수이며, 여기서, N이 2 이상의 정수인 경우, N개의 [ ]내의 구조식은 동일할 수도 상이할 수도 있고, r은, 각각 독립적으로 0~2의 정수이다.)The present invention provides a compound represented by the following formula (0).

(In the formula (0), R ^Y is a hydrogen atom, R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each R ^T independently represents an optionally substituted group having 1 to 30 carbon atoms An alkyl 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, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, A thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R ^T is a hydroxyl group , And at least one of R ^T represents an alkenyl group having 2 to 30 carbon atoms, X represents an oxygen atom, a sulfur atom, a single bond or a non-condensed group, m is independently an integer of 0 to 9, Lt; / RTI > is an integer from 2 to 9 or at least 2 Is an integer of 1 to 9, and N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas within N [] may be the same or different, It is an integer of 2.

Description

COMPOUND, RESIN, COMPOSITION, AND RESIST PATTERN FORMING METHOD

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

In the production of semiconductor devices, fine processing by lithography using a photoresist material has been performed. However, along with the increase in the integration and the speed of LSI, there has been a demand for further miniaturization by the pattern rule. In addition, the light source for lithography used for forming a resist pattern is short-wavelength from a KrF excimer laser (248 nm) to an ArF excimer laser (193 nm), and the introduction of extreme ultraviolet light (EUV, 13.5 nm) is also expected.

However, in the conventional lithography using a high molecular weight resist material, the molecular weight is as large as about 10,000 to 100,000 and the molecular weight distribution is wide, so that roughness occurs on the pattern surface and control of the pattern dimension becomes difficult, . To date, various low-molecular-weight resist materials have been proposed in order to impart a resist pattern with higher resolution. The low molecular weight resist material is expected to give a resist pattern with high resolution and low roughness because of its small molecular size.

At present, various such low-molecular-weight resist materials are known. For example, there has been proposed an alkali developing type negative-tone radiation-sensitive composition (see, for example, Patent Document 1 and Patent Document 2) using a low molecular weight polynuclear polyphenol compound as a main component, As a candidate for a material, there has been proposed an alkali developing type negative-tone radiation-sensitive composition (for example, see Patent Document 3 and Non-Patent Document 1) using a low molecular weight cyclic polyphenol compound as a main component. Further, it is known that a polyphenol compound as a base compound of a resist material can impart a high heat resistance with a low molecular weight, and is useful for improving the resolution and roughness of a resist pattern (see, for example, Non-Patent Document 2 ).

The present inventors have proposed a resist composition (see, for example, Patent Document 4) containing a compound having a specific structure and an organic solvent as a material which is excellent in etching resistance and soluble in a solvent and applicable to a wet process so far .

Further, when the resist pattern becomes finer, there arises a problem such as a problem of resolution or a collapse of the resist pattern after development, so that it is required to reduce the thickness of the resist. However, when the thinning of the resist is simply performed, it becomes difficult to obtain a film thickness of a resist pattern sufficient for substrate processing. For this reason, a process for forming a resist underlayer film between a resist and a semiconductor substrate to be processed as well as a resist pattern, and for providing the resist underlayer film with a function as a mask at the time of processing the substrate is also required.

At present, various known resist undercoat films for such processes are known. For example, unlike a conventional resist underlayer film having a high etching rate, a resist underlayer film having a selectivity ratio of a dry etching rate close to that of a resist is realized. When a predetermined energy is applied, a terminal group is eliminated and a sulfonic acid residue (For example, refer to Patent Document 5). The lower layer film forming material for a multi-layer resist process containing a solvent has been proposed. A resist underlayer film material containing a polymer having a specific repeating unit has been proposed to realize a resist underlayer film having a selectivity of a dry etching rate lower than that of a resist film (for example, refer to Patent Document 6 ). Furthermore, it is an object of the present invention to realize a resist underlayer film having a selectivity of a dry etching rate lower than that of a semiconductor substrate, and a polymer obtained by copolymerizing a repeating unit of acenaphthylene and a repeating unit having a substituted or unsubstituted hydroxy group (For example, refer to Patent Document 7).

On the other hand, an amorphous carbon lower layer film formed by CVD using methane gas, ethane gas, acetylene gas, or the like as a raw material is well known as a material having high etching resistance in such a resist lower layer film. However, from the viewpoint of processes, a resist underlayer film material capable of forming a resist underlayer film in a wet process such as spin coating or screen printing is required.

The present inventors have also found that a composition for forming a lithographic underlayer film containing a compound having a specific structure and an organic solvent as a material which is excellent in etching resistance and is high in heat resistance and soluble in a solvent and applicable to a wet process , Patent Document 8).

Further, the method of forming the intermediate layer used in the formation of the resist lower layer film in the three-layer process includes, for example, a method of forming a silicon nitride film (see, for example, Patent Document 9) (See, for example, Patent Document 10) are known. As an intermediate layer material for a three-layer process, a material containing a silsesquioxane-based silicon compound is known (see, for example, Patent Documents 11 and 12).

(For example, see Patent Documents 13 to 14) and polyphenols having a specific structure derived from an allyl group (for example, Patent Document 15 ) Has been proposed.

Japanese Patent Application Laid-Open No. 2005-326838 Japanese Patent Application Laid-Open No. 2008-145539 Japanese Patent Application Laid-Open No. 2009-173623 International Publication No. 2013/024778 Japanese Patent Application Laid-Open No. 2004-177668 Japanese Patent Application Laid-Open No. 2004-271838 Japanese Patent Application Laid-Open No. 2005-250434 International Publication No. 2013/024779 Japanese Patent Application Laid-Open No. 2002-334869 International Publication No. 2004/066377 Japanese Patent Application Laid-Open No. 2007-226170 Japanese Patent Application Laid-Open No. 2007-226204 Japanese Patent Application Laid-Open No. 2010-138393 Japanese Patent Application Laid-Open No. 2015-174877 International Publication No. 2014/123005

T. Nakayama, M. Nomura, K. Haga, M. Ueda: Bull.Chem.Soc.Jpn., 71, 2997 (1998) Shinji Okazaki, et al. 22 "New Development of Photoresist Material Development" by MC Corporation, September 2009, p.211-259

As described above, conventionally, there have been proposed a film forming composition for lithography for a large number of resist applications and a film forming composition for lithography for a lower layer film application, but it has a high solvent solubility to which a wet process such as a spin coating process or a screen printing process can be applied In addition, there is no compatibility with heat resistance and etching resistance at a high level, and development of new materials is required.

In addition, a large number of compositions for optical members have been proposed in the past, but they have not been compatible with heat resistance, transparency, and refractive index in a high dimension, and development of new materials is required.

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and an object of the present invention is to provide a photoresist and a photoresist film which are applicable to a wet process and which are excellent in heat resistance, solubility and etching resistance, , And compositions.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies in order to solve the problems of the prior art, and as a result, they have found that a compound or a resin having a specific structure can solve the problems of the prior art, and have completed the present invention .

That is, the present invention is as follows.

[One]

(0). ≪ / RTI >

[Chemical Formula 1]

(0)

(In the formula (0), R ^Y is a hydrogen atom,

R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms,

R ^T each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond or an ester bond Wherein at least one of R ^T is a hydroxyl group and at least one of R ^T is an alkenyl group having 2 to 30 carbon atoms,

X represents an oxygen atom, a sulfur atom, a single bond or a non-condensed,

m is independently an integer of 0 to 9, provided that at least one of m is an integer of 2 to 9, or at least two of m is an integer of 1 to 9,

N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas within N [] may be the same or different,

r is independently an integer of 0 to 2.)

[2]

The compound according to [1], wherein the compound represented by the formula (0) is a compound represented by the following formula (1).

(2)

(One)

(In the formula (1), R ⁰ is the same as R ^Y ,

R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms,

R ² to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond Or at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms,

m ² and m ³ are each independently an integer of 0 to 8,

m ⁴ and m ⁵ are each independently an integer of 0 to 9 with the proviso that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time, m ² , m ³ , m ⁴ and m ⁵ At least one of them is an integer of 2 to 8 or 2 to 9, or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9,

When n is an integer of 2 or more, the structural formulas within n [] may be the same or different,

and p ² to p ⁵ each independently denote the same as r.

[3]

The compound according to [1], wherein the compound represented by the formula (0) is a compound represented by the following formula (2).

(3)

(2)

(In the formula (2), R ^0A is the same as the above R ^Y ,

R ^1A is an n ^A -valent group or a single bond having 1 to 30 carbon atoms,

R ^2A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond or an ester bond Wherein at least one of R ^2A is at least one hydroxyl group and at least one of R ^2A is an alkenyl group having 2 to 30 carbon atoms,

n ^A is a consensus with the above N, wherein, when n ^A is an integer of 2 or more, the structural formulas in n ^A [] may be the same or different,

X ^A represents an oxygen atom, a sulfur atom, a single bond or a non-condensed,

m ^2A is independently an integer of 0 to 7, provided that at least one of m ^2A is an integer of 2 to 7 or at least two of m ^2A is an integer of 1 to 7,

q ^A are each independently 0 or 1.)

[4]

The compound according to [2], wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

[Chemical Formula 4]

(1-1)

(In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are the same as above,

R ⁶ to R ⁷ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, An atom, a nitro group, an amino group, a carboxylic acid group or a thiol group, wherein at least one of R ⁶ to R ⁷ is an alkenyl group having 2 to 30 carbon atoms,

R ¹⁰ to R ¹¹ are each independently a hydrogen atom,

m ⁶ and m ⁷ are each independently an integer of 0 to 7 with the proviso that m ⁴ , m ⁵ , m ⁶ and m ⁷ do not become 0 at the same time.

[5]

The compound according to [4], wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).

[Chemical Formula 5]

(1-2)

(Wherein R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are as defined above,

R ⁸ to R ⁹ are as defined above for R ⁶ to R ⁷ ,

R ¹² to R ¹³ are as defined above for R ¹⁰ to R ¹¹ ,

m ⁸ and m ⁹ are each independently an integer of 0 to 8, provided that m ⁶ , m ⁷ , m ⁸ and m ⁹ do not become 0 at the same time.

[6]

The compound according to [3], wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).

[Chemical Formula 6]

(2-1)

(In the formula (2-1), R ^0A , R ^{1 A} , n ^A , q ^A and X ^A are as defined above,

R ^3A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, An amino group, a carboxylic acid group or a thiol group, wherein at least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms,

R ^4A are each independently a hydrogen atom,

m ^6A are each independently an integer of 0 to 5.)

[7]

A resin obtained by using the compound described in [1] as a monomer.

[8]

The resin according to [7], having a structure represented by the following formula (3).

(7)

(3)

(In the formula (3), L represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, An alkoxylene group or a single bond having 1 to 30 carbon atoms, and the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,

R ⁰ is synonymous with R ^Y above,

R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms,

R ² to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond Or an ester bond, wherein at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms,

m ² and m ³ are each independently an integer of 0 to 8,

m ⁴ and m ⁵ are each independently an integer of 0 to 9 with the proviso that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time, m ² , m ³ , m ⁴ and m ⁵ Is an integer of 2 to 8 or 2 to 9, or at least two of m ² , m ³ , m ⁴ and m ⁵ is an integer of 1 to 8 or 1 to 9.)

[9]

The resin according to [7], having a structure represented by the following formula (4).

[Chemical Formula 8]

(4)

(In the formula (4), L represents a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond,

R ^0A is synonymous with R ^Y above,

R ^1A is an n ^A -valent group or a single bond having 1 to 30 carbon atoms,

R ^2A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond or an ester bond , Wherein at least one of R ^2A is a hydroxyl group, and at least one of R ^2A is an alkenyl group having 2 to 30 carbon atoms,

n ^A is a consensus with the above N, wherein, when n ^A is an integer of 2 or more, the structural formulas in n ^A [] may be the same or different,

X ^A represents an oxygen atom, a sulfur atom, a single bond or a non-condensed,

m ^2A is independently an integer of 0 to 7, provided that at least one of m ^2A is an integer of 2 to 7 or at least two of m ^2A is an integer of 1 to 7,

q ^A are each independently 0 or 1.)

[10]

A composition comprising at least one compound selected from the group consisting of the compounds described in any one of [1] to [6] and the resins described in any one of [7] to [9].

[11]

The composition according to [10], further comprising a solvent.

[12]

The composition according to [10] or [11], further comprising an acid generator.

[13]

The composition according to any one of [10] to [12], further comprising a crosslinking agent.

[14]

Wherein the crosslinking agent is at least one selected from the group consisting of phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds and azide compounds The composition according to [13].

[15]

The composition according to [13] or [14], wherein the crosslinking agent has at least one allyl group.

[16]

The composition according to any one of [13] to [15], wherein the content of the crosslinking agent is 0.1 to 50 mass% of the total mass of the solid component.

[17]

The composition according to any one of [13] to [16], further comprising a crosslinking accelerator.

[18]

The composition according to [17], wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.

[19]

The composition according to [17] or [18], wherein the content of the crosslinking accelerator is 0.1 to 5 mass% of the total mass of the solid component.

[20]

The composition according to any one of [10] to [19], further comprising a radical polymerization initiator.

[21]

The composition according to any one of [10] to [20], wherein the radical polymerization initiator is 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.

[22]

The composition according to any one of [10] to [21], wherein the content of the radical polymerization initiator is 0.05 to 25% by mass of the total mass of the solid component.

[23]

The composition according to any one of [10] to [22], which is used for film formation for lithography.

[24]

The composition according to any one of [10] to [22], which is used for resist permanent film formation.

[25]

The composition according to any one of [10] to [22], which is used for forming an optical component.

[26]

A step of forming a photoresist layer on the substrate using the composition described in [23], and then irradiating a predetermined region of the photoresist layer with radiation to perform development.

[27]

Forming a lower layer film on the substrate using the composition described in [23], forming at least one photoresist layer on the lower layer film, irradiating a predetermined region of the photoresist layer with radiation, Thereby forming a resist pattern.

[28]

An undercoat film is formed on a substrate using the composition described in [23], an interlayer film is formed on the undercoat film using a resist interlayer film material, and at least one photoresist layer is formed on the interlayer film And then the resist pattern is used as a mask to etch the intermediate layer film, and the obtained intermediate layer film pattern is etched using an etching mask And etching the substrate using the obtained lower layer film pattern as an etching mask to form a pattern on the substrate.

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

Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as " present embodiment ") will be described. The following embodiments are illustrative of the present invention, and the present invention is not limited to the embodiments.

The compound, the resin, and the composition containing the same in the present embodiment are useful for forming a photoresist underlayer film which is applicable to a wet process and is excellent in heat resistance and etching resistance. In addition, since the composition of the present embodiment uses a compound or resin having a specific structure and high heat resistance and solvent solubility, deterioration of the film at the time of high-temperature baking is suppressed, and the etching resistance against oxygen plasma etching, And a lower layer film can be formed. In addition, when a lower layer film is formed, adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed.

Furthermore, it is also useful as various optical forming compositions in that the refractive index is high and the coloring by a wide range of heat treatment from low temperature to high temperature is suppressed.

[Compound represented by formula (0)

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

[Chemical Formula 9]

(0)

(In the formula (0), R ^Y is a hydrogen atom,

R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms,

R ^T each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond or an ester bond Wherein at least one of R ^T is a hydroxyl group and at least one of R ^T is an alkenyl group having 2 to 30 carbon atoms,

X represents an oxygen atom, a sulfur atom, a single bond or a non-condensed,

m is independently an integer of 0 to 9, provided that at least one of m is an integer of 2 to 9, or at least two of m is an integer of 1 to 9,

N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas within N [] may be the same or different,

r is independently an integer of 0 to 2.)

R ^Y is a hydrogen atom. The alkyl group may be a linear, branched or cyclic alkyl group. Since R ^Y is a hydrogen atom, excellent heat resistance and solvent solubility can be imparted.

R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each aromatic ring is bonded via R ^Z. N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas within N [] may be the same or different. The N-valent group is an alkyl group having 1 to 60 carbon atoms when N = 1, an alkylene group having 1 to 30 carbon atoms when N = 2, an alkane-containing group having 2 to 60 carbon atoms when N = 3, = 4 represents an alkanetetrayl group having 3 to 60 carbon atoms. The N-valent groups include, for example, those having a straight-chain hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group. The N-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms.

R ^T each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group and a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may be substituted by an ether bond, a ketone bond or an ester bond , Wherein at least one of R ^T is a hydroxyl group and at least one of R ^T includes an alkenyl group having 2 to 30 carbon atoms. On the other hand, the alkyl group, alkenyl group and alkoxy group may be a straight chain, branched or cyclic group.

X is an oxygen atom, a sulfur atom, a single bond or a non-condensed, and when X is an oxygen atom or a sulfur atom, it is preferable because it tends to exhibit high heat resistance and is more preferably an oxygen atom. From the viewpoint of solubility, X is preferably a non-crosslinked one. M is an integer of 0 to 9, and at least one of m is an integer of 2 to 9, or at least two of m is an integer of 1 to 9.

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

[Compound represented by the formula (1)

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

[Chemical formula 10]

(One)

In the above formula (1), R ⁰ is the same as R ^Y and is a hydrogen atom. When R < ⁰ > is a hydrogen atom, the heat resistance is relatively high, and the solvent solubility tends to be improved.

R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms, and each aromatic ring is bonded via R ¹ .

R ² to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond Or an ester bond, wherein at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms.

m ² and m ³ each independently represent an integer of 0 to 8; m ⁴ and m ⁵ each independently represent an integer of 0 to 9; Provided that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time. at least one of m ² , m ³ , m ⁴ and m ⁵ is an integer of 2 to 8 or 2 to 9, or at least two of m ² , m ³ , m ⁴ and m ⁵ are 1 to 8 or 1 to 9 It is an integer.

n agrees with N, and is an integer of 1 to 4. Here, when n is an integer of 2 or more, the structural formulas within n [] may be the same or different.

p ² to p ⁵ each independently represent an integer of 0 to 2,

On the other hand, the alkyl group, alkenyl group and alkoxy group may be a straight chain, branched or cyclic group.

The n-valent group is an alkyl group having 1 to 60 carbon atoms when n = 1, an alkylene group having 1 to 30 carbon atoms when n = 2, an alkane group having 2 to 60 carbon atoms when n = 3 And n = 4 represents an alkanetetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a straight-chain hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group. The n-valent group may have an aromatic group having 6 to 60 carbon atoms.

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

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

In addition, since the solubility in a safe solvent is high and the heat resistance and the etching resistance are good, a resist pattern forming composition for lithography containing the compound represented by the formula (1) can give a good resist pattern shape.

Furthermore, even in the case of a substrate having a step (particularly, a minute space or a hole pattern or the like) at a relatively low molecular weight and low viscosity, it is easy to increase the flatness of the film while uniformly filling the corners of the step, The lower layer film forming composition for lithography used has favorable buried and planarized characteristics. In addition, since it is a compound having a relatively high carbon concentration, high etching resistance can also be imparted.

In addition, since the aromatic densities are high, the refractive index is high and coloration is suppressed even by a wide range of heat treatments from a low temperature to a high temperature. Among them, a compound having a quaternary carbon is preferable from the viewpoints of suppressing the oxidative decomposition of the compound to suppress coloration, and improving the heat resistance and solvent solubility. Examples of the optical component include a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast enhancement lens and the like), a retardation film, a film for electromagnetic wave shielding, A solder resist for a flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

The compound represented by the formula (1) is more preferably a compound represented by the following formula (1-1) from the viewpoints of easiness of crosslinking and solubility in an organic solvent.

(11)

(1-1)

In the formula (1-1)

R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are as defined above,

R ⁶ to R ⁷ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, An atom, a nitro group, an amino group, a carboxylic acid group or a thiol group, wherein at least one of R ⁶ to R ⁷ is an alkenyl group having 2 to 30 carbon atoms,

R ¹⁰ to R ¹¹ are each independently a hydrogen atom,

m ⁶ and m ⁷ are each independently an integer of 0 to 7 with the proviso that m ⁴ , m ⁵ , m ⁶ and m ⁷ do not become 0 at the same time.

The compound represented by the formula (1-1) is more preferably a compound represented by the following formula (1-2) from the viewpoints of ease of further crosslinking and solubility in an organic solvent.

[Chemical Formula 12]

(1-2)

In the formula (1-2)

^{R 0, R 1, R 6} , R 7, R 10, R 11, n, p 2 ~ p 5, m 6 and m is ^7, and the accept and,

R ⁸ to R ⁹ are as defined above for R ⁶ to R ⁷ ,

R ¹² to R ¹³ are as defined above for R ¹⁰ to R ¹¹ ,

m ⁸ and m ⁹ are each independently an integer of 0 to 8; Provided that m ⁶ , m ⁷ , m ⁸ and m ⁹ do not become 0 at the same time.

The compound represented by the formula (1-1) is more preferably a compound represented by the following formula (1a) in view of the feedability of the starting material.

[Chemical Formula 13]

(1a)

In the formula (1a), R ⁰ to R ⁵ , m ² to m ⁵ and n are synonymous with those described in the formula (1).

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

[Chemical Formula 14]

(1b)

In the formula ^{(1b), R 0, R} 1, R 4, R 5, m 4, m 5, n is an agreement to that described in the formula ^{(1), R 6, R} 7, R 10, R 11, m ⁶ , and m ⁷ are as defined in the above formula (1-1).

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

[Chemical Formula 15]

(1b ')

In the formula ^{(1b '), R 0,} R 1, R 4, R 5, m 4, m 5, n is an agreement to that described in the formula ^{(1), R 6, R} 7, R 10, R 11 , m ⁶ and m ⁷ are the same as those described in the above formula (1-1).

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

[Chemical Formula 16]

(1c)

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

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

[Chemical Formula 17]

(1c ')

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

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

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

X is the same as that described in formula (0), R ^{T '} is the same as R ^T described in formula (0), and m is independently an integer of 0 to 9, at least one of m is an integer of 2 to 9 or at least two of m is an integer of 1 to 9. [ Wherein at least one of R ^{T '} is a hydroxyl group, and at least one of R ^T' is an alkenyl group having 2 to 30 carbon atoms.

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

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

(36)

In the above formula, X is the same as that described in formula (0), and R ^{Y '} and R ^Z' are the same as R ^Y _and R ^Z described in formula (0). Each R ^4A is independently a hydrogen atom.

Specific examples of the compound represented by the formula (1) are shown below, but the compound is not limited thereto.

(37)

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

Among these compounds, R ² , R ³ , R ⁴ and R ⁵ are the same as those described in the formula (1). m ² and m ³ are integers of 0 to 8, and m ⁴ and m ⁵ are integers of 0 to 9.

Provided that at least one selected from R ² , R ³ , R ⁴ and R ⁵ is a hydroxyl group and at least one selected from R ² , R ³ , R ⁴ and R ⁵ is an alkenyl group having 2 to 30 carbon atoms . m ² , m ³ , m ⁴ , and m ⁵ do not become 0 at the same time.

The compound represented by the above formula (1), it is in view of the solubility in a further organic solvent, the following formula (BiF-1) ~ a compound represented by (BiF-5), particularly preferably (R ¹⁰ ~ of the embodiments R < ¹³ > is the same as that described above).

[Chemical Formula 45]

(BiF-1)

(46)

(BiF-2)

(47)

(BiF-3)

(48)

(BiF-4)

(49)

(BiF-5)

In the formulas (BiF-1) to (BiF-5), R ^{6 '} to R ^9' each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol group, in which at least one of R ^{6 '} to R ^9' is an alkyl group having a carbon number of from 1 to 30, an alkenyl group having from 2 to 30 carbon atoms which may have a substituent, 2 to 30 alkenyl groups, and R ¹⁰ to R ¹³ are the same as those described in Formula (1c).

(50)

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), and each R ¹⁴ independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an alkyl group having 6 to 30 carbon atoms An alkoxy group having 1 to 30 carbon atoms, a halogen atom, a thiol group, m ¹⁴ is an integer of 0 to 5, m ^{14 '} is an integer of 0 to 4, m ^{14 "} Is an integer of 0 to 3.

R ¹⁴ represents a group selected from the group consisting of, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, A chlorine atom, a bromine atom, an iodine atom, a thiol group, a bromine atom, a bromine atom, an iodine atom, a thiol group, a cyano group, a nitro group, an anthracene group, a pyrenyl group, a biphenyl group, .

Each of the examples of R < ¹⁴ > includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), and R ¹⁵ represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, An alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.

R ¹⁵ represents a group selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, A chlorine atom, a bromine atom, an iodine atom, a thiol group, a bromine atom, a bromine atom, an iodine atom, a thiol group, a cyano group, a nitro group, an anthracene group, a pyrenyl group, a biphenyl group, .

Each of the examples of R < ¹⁵ > includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

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

(51)

(52)

^Wherein R ^0A is the same as that of the formula R ^Y , is the same as R ^{1A '} and R ^Z, and R ¹⁰ to R ¹³ are the same as those described in the formula (1-2).

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

R ¹⁴ represents a group selected from the group consisting of, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, An alkoxy group, a methoxy group, an ethoxy group, a triacontic group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a thiol group.

Each of the examples of R < ¹⁴ > includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

(53)

(54)

(55)

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), and R ¹⁵ represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, An alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.

R ¹⁵ represents a group selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, An alkoxy group, a methoxy group, an ethoxy group, a triacontic group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a thiol group.

Each of the examples of R < ¹⁵ > includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

(56)

(57)

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), R ¹⁶ represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, a divalent An aryl group, or a divalent alkenyl group having 2 to 30 carbon atoms.

R ¹⁶ is a group selected from the group consisting of a methylene group, an ethylene group, a propene group, a butene group, a pentene group, a hexene group, a heptene group, an octene group, a nonene group, a decene group, an undecene group, a dodecene group, a triacontene group, A cycloheptene group, a cyclopentene group, a cyclohexene group, a cycloheptene group, a cycloheptene group, a cycloheptene group, a cycloheptene group, a cyclooctene group, a cyclonone group, a cyclodecene group, a cyclododecene group, a cyclododecene group, A divalent naphthyl group, a divalent anthracene group, a divalent heptasene group, a divalent vinyl group, a divalent allyl group, and a divalent trialkontenyl group can be given.

Each of the examples of R < ¹⁶ > includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

(58)

[Chemical Formula 59]

(60)

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

R ¹⁴ represents a group selected from the group consisting of, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, An alkoxy group, a methoxy group, an ethoxy group, a triacontic group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a thiol group.

Each of the examples of R < ¹⁴ > includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

(61)

(62)

(63)

≪ EMI ID =

(65)

(66)

In the formula, R ¹⁰ to R ¹³ are the same as those described in the formula (1-2). The above formula is preferable from the viewpoint of the heat resistance of the side having the dibenzo xanthene skeleton.

The above compound is more preferably a compound represented by the following in view of the availability of the starting material.

(67)

(68)

(69)

(70)

(71)

(72)

(73)

≪ EMI ID =

(75)

[Formula 76]

[Formula 77]

(78)

(79)

(80)

[Formula 81]

(82)

In the formula, R ¹⁰ to R ¹³ are the same as those described in the formula (1-2). The above formula is preferable from the viewpoint of the heat resistance of the side having the dibenzo xanthene skeleton.

The above formula is preferably expressed by the following structure from the viewpoint of raw material availability, and it is more preferable that the compound is a compound having a dibenzo xanthene skeleton from the viewpoint of heat resistance.

(83)

^Wherein R ^{0A corresponds} to the formula R ^Y , R ^{1A 'corresponds} to R ^Z, and R ¹⁰ to R ¹³ correspond to those described in the formula (1-2). The above formula is more preferable from the viewpoint of heat resistance, since it is a compound having a xanthene skeleton.

(84)

(85)

≪ EMI ID =

[Chemical Formula 87]

[Formula 88]

(89)

(90)

[Formula 91]

≪ EMI ID =

≪ EMI ID =

(94)

≪ EMI ID =

≪ EMI ID =

[Formula 97]

(98)

[Formula 99]

(100)

(101)

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

In the above formulas, R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), and R ¹⁴ , R ¹⁵ , R ¹⁶ , m ¹⁴ and m ^{14 '} are as defined above.

[Process for producing a compound represented by the formula (0)] [

The compound represented by the formula (0) in this embodiment can be appropriately synthesized by applying a known technique, and the synthesis method thereof is not particularly limited. Hereinafter, the compound represented by the formula (0) will be described as an example of the compound represented by the formula (1).

For example, a polyphenol compound is obtained by subjecting a non-phenol, a binaphthol or a nonanthracene and a corresponding aldehyde to polycondensation reaction under an atmospheric pressure under an acid catalyst to obtain a polyphenol compound, which is then reacted with at least one phenolic hydroxyl group , Introducing an allyl group, and then heating to carry out the Clagen transition. Further, if necessary, it may be carried out under pressure.

The timing for introducing the allyl group may be introduced before the condensation reaction, after the step, or after the production of the resin described later.

Examples of the non-phenol include biphenol, methyl biphenol, methoxybinol, and the like, but they are not particularly limited thereto. These may be used singly or in combination of two or more. Of these, it is more preferable to use biphenol from the viewpoint of stable supply of raw materials.

Examples of the non-naphthols include, but are not limited to, binaphthol, methyl binaphthol, methoxybiphentol and the like. These may be used singly or in combination of two or more. Of these, it is more preferable to use binaphthol from the viewpoint of increasing the carbon atom concentration and improving the heat resistance.

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethyl But are not limited to, benzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthalaldehyde, anthracene carbaldehyde, phenanthrenecarbaldehyde, pyrencarboaldehyde, furfural and the like. These may be used singly or in combination of two or more. Among them, from the viewpoint of imparting high heat resistance, it is preferable to use at least one of benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, It is preferable to use aldehyde, anthracene carbaldehyde, phenanthrenecarboaldehyde, pyrenecarboaldehyde and furfural. From the viewpoint of improving the etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethyl Those using benzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthalaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural It is more preferable.

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

The acid catalyst to be used in the reaction can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known and include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; But are not limited to, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, Organic acids such as sulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; But are not limited to, Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride, and solid acids such as silicotungstic acid, tungstic acid, silicomolybdic acid or phosphomolybdic acid. Of these, from the viewpoint of production, organic acids and solid acids are preferable, and hydrochloric acid or sulfuric acid is more preferably used from the viewpoint of production easiness such as easy availability and easy handling. On the other hand, 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 to be used can be suitably set according to the kinds of raw materials and catalyst to be used and furthermore the reaction conditions, and is not particularly limited, but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material.

In the reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction between the aldehyde to be used and the non-phenol, binaphthol or nonanthracene diol proceeds, and can be appropriately selected from known ones. Examples of the reaction solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or a mixed solvent thereof. On the other hand, one solvent may be used alone, or two or more solvents may be used in combination.

The amount of these reaction solvents to be used can be suitably set according to the kind of raw materials and catalyst to be used and furthermore the reaction conditions, and 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-mentioned reaction can be appropriately selected according to the reactivity of the reaction raw material and is not particularly limited, but is usually in the range of 10 to 200 ° C.

In order to obtain a polyphenol compound, the reaction temperature is preferably high, and specifically preferably in the range of 60 to 200 ° C. On the other hand, as the reaction method, a known method can be appropriately selected and used. Without particular limitation, there can be mentioned a method in which a non-phenol, a binaphthol or a nonanthracene diol, an aldehyde or a catalyst are added all at once, Or an anthracene diol or an aldehyde is added dropwise in the presence of a catalyst. After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to the conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts existing in the system, by employing a general method such as raising the temperature of the reaction pot to 130 to 230 ° C and removing volatile components at about 1 to 50 mmHg, The phosphorus compound can be isolated.

Preferable reaction conditions are as follows: 1 mol to excess amount of non-phenols, binaphthol or nonanthracene diol, and 0.001 to 1 mol of an acid catalyst per mole of aldehyde are reacted at 50 to 150 DEG C for 20 minutes 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 a reaction product, the reaction product is cooled to room temperature, filtered and separated, and the resulting solid is filtered, dried and then purified by column chromatography Separation and purification, solvent removal, filtration and drying are carried out to obtain the target compound represented by the above formula (1).

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

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

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

Thereafter, by heating, the allyl group introduced into the phenolic hydroxyl group can be transferred by the Clagen transition.

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

[Resin obtained by using the compound represented by the formula (0) as a monomer]

The compound represented by the above formula (0) can be used as it is as a composition used for forming a film for lithography and forming an optical component (hereinafter, simply referred to as " composition "). Further, a resin obtained by using the compound represented by the formula (0) as a monomer may be used as the composition. The resin is obtained, for example, by reacting a compound represented by the formula (0) with a compound having a crosslinking reactivity. Hereinafter, a resin obtained by using a compound represented by the formula (0) as a monomer is described as an example of a resin obtained by using a compound represented by the formula (1) as a monomer.

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

(108)

(3)

In formula (3), L represents an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, an alkoxysilane group having 1 to 30 carbon atoms which may have a substituent, And the alkylene group, the arylene group, and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond. The alkylene group and alkoxylene group may be a straight chain, branched or cyclic group.

^{R 0, R 1, R 2} ~ R 5, m 2 and m ^3, m ⁴ and ^{m 5, p 2 ~ p 5} , n is as agreed in the formula (1).

M ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time, and at least one of m ² , m ³ , m ⁴ and m ⁵ is an integer of 2 to 8 or 2 to 9 or m ² , at least two of m ³ , m ⁴ and m ⁵ are an integer of 1 to 8 or 1 to 9, at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is a To 30 carbon atoms.

[Process for producing a resin obtained by using a compound represented by the formula (1) as a monomer]

The resin in the present embodiment is obtained by reacting the compound represented by the formula (1) with a compound having a crosslinking reactivity. As the compound having a crosslinking reactivity, known compounds can be used as long as they can oligomerize or polymerize the compound represented by the formula (1). Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates and unsaturated hydrocarbon group-containing compounds Do not.

Specific examples of the resin having the structure represented by the formula (3) include, for example, by condensation reaction of the compound represented by the formula (1) with an aldehyde and / or ketone, which is a crosslinkable compound, And novolac resins.

Examples of the aldehyde used in the novolak of the compound represented by the formula (1) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde Benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, hydroxymethylbenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, But are not particularly limited to these. Examples of the ketone include the above-mentioned ketones. Of these, formaldehyde is more preferable. On the other hand, these aldehydes and / or ketones may be used singly or in combination of two or more kinds. The amount of the aldehyde and / or ketone to be used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per 1 mole of the compound represented by the formula (1).

In the condensation reaction of the compound represented by the formula (1) with an aldehyde and / or a ketone, an acid catalyst may be used. The acid catalyst to be used here can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known and include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; But are not limited to, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, Organic acids such as sulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; But are not limited to, Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride, and solid acids such as silicotungstic acid, tungstic acid, silicomolybdic acid or phosphomolybdic acid. Of 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 easiness such as easy availability and ease of handling. On the other hand, 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 to be used can be suitably set according to the kinds of raw materials and catalyst to be used and furthermore the reaction conditions, and is not particularly limited, but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material. However, it is preferable to use a compound selected from the group consisting of indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, In the case of the copolymerization reaction with a compound having a non-conjugated double bond such as vinyl norborna-2-ene,? -Pinene,? -Pinene and limonene, an aldehyde is not necessarily required.

In the condensation reaction of the compound represented by the formula (1) with an aldehyde and / or a ketone, a reaction solvent may be used. The reaction solvent in the polycondensation is not particularly limited and may be appropriately selected from known ones. Examples of the solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, Mixed solvents, and the like. On the other hand, one solvent may be used alone, or two or more solvents may be used in combination.

The amount of these solvents to be used can be suitably set according to the type of raw material and catalyst to be used, furthermore, reaction conditions, etc., and is not particularly limited, but is preferably in the range of 0 to 2,000 parts by mass based on 100 parts by mass of the reaction raw material. Further, the reaction temperature can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 占 폚. On the other hand, as the reaction method, a known method can be appropriately selected and used. Without particular limitation, a method of collectively introducing the compound represented by the formula (1), the aldehyde and / or the ketone and the catalyst, 1) or an aldehyde and / or a ketone is added dropwise in the presence of a catalyst.

After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to the conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts existing in the system, by employing a general method such as raising the temperature of the reaction pot to 130 to 230 ° C and removing volatile components at about 1 to 50 mmHg, The novolak resin can be isolated.

Here, the resin having the structure represented by the formula (3) may be a homopolymer of the compound represented by the formula (1), or may be a copolymer with other phenols. Examples of the copolymerizable phenol include phenol, cresol, dimethyl phenol, trimethyl phenol, butyl phenol, phenyl phenol, diphenyl phenol, naphthyl phenol, resorcinol, methyl resorcinol, catechol, , Methoxyphenol, methoxyphenol, propylphenol, pyrogallol, thymol and the like, but they are not particularly limited thereto.

In addition to the above-mentioned other phenols, the resin having the structure represented by the formula (3) may be a copolymer obtained by copolymerizing with a polymerizable monomer. Examples of such copolymerizable monomers include monomers such as naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, But are not limited to, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, novornadiene, vinylnononane, pinene, limonene, and the like. On the other hand, the resin having the structure represented by the formula (3) may be a copolymer of two or more atoms (for example, a two to four member system) of the compound represented by the formula (1) Even if a copolymer of two or more atoms (for example, a two to four member system) of the compound represented by the formula (1) and the above-mentioned copolymerizable monomer is used, the compound represented by the formula (1) (For example, a 3 to 4 member system) copolymer with one copolymerizable monomer may be used.

The molecular weight of the resin having the structure represented by the formula (3) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, more preferably 750 to 20,000. From the viewpoint of increasing the crosslinking efficiency and suppressing the volatile components in the baking, the resin having the structure represented by the formula (3) has a dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of 1.2 to 7 Is preferably within the range. On the other hand, the Mw and Mn can be obtained by the methods described in Examples described later.

The resin having the structure represented by the formula (3) preferably has a high solubility in a solvent from the viewpoint that the application of the wet process becomes easier. More specifically, when 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) are used as a solvent, the solubility in the solvent is preferably 10 mass% or more. Here, the solubility in PGME and / or PGMEA is defined as " mass of resin / (mass of resin + mass of solvent) x 100 (mass%) ". For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA is " 10 mass% or more ", and when it is not dissolved, it is less than 10 mass%.

[Compound represented by formula (2)

The compound represented by the formula (0) in the present embodiment is preferably a compound represented by the following formula (2) from the viewpoints of heat resistance and solvent solubility.

(109)

(2)

In formula (2), R ^0A is the same as R ^Y and is a hydrogen atom.

R ^1A is an n ^A -valent group or a single bond having 1 to 30 carbon atoms,

R ^2A each independently represents a linear, branched or cyclic alkyl group of 1 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms which may have a substituent, an aryl group of 2 to 30 carbon atoms which may have a substituent An alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group, An ether bond, a ketone bond or an ester bond, wherein at least one of R ^2A is a hydroxyl group, and at least one of R ^2A is an alkenyl group having 2 to 30 carbon atoms.

n ^A is the same as the above N and is an integer of 1 to 4. In the formula (2), when n ^A is an integer of 2 or more, the structural formulas within n ^A [] may be the same or different.

X ^A each independently represents an oxygen atom, a sulfur atom, a single bond or a non-condensed group. Here, since X ^A tends to exhibit excellent heat resistance, it is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom. From the viewpoint of solubility, X ^A is preferably a non-crosslinked one.

m ^2A are each independently an integer of 0 to 6; Provided that at least one m ^2A is an integer of 2 to 6 or at least two m ^2A is an integer of 1 to 6.

q ^A is independently 0 or 1;

The n-valent group is an alkyl group having 1 to 60 carbon atoms when n = 1, an alkylene group having 1 to 30 carbon atoms when n = 2, an alkane group having 2 to 60 carbon atoms when n = 3 And n = 4 represents an alkanetetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a straight-chain hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group. The n-valent group may have an aromatic group having 6 to 60 carbon atoms.

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

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

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

In addition, since the solubility in a safe solvent is high and the heat resistance and the etching resistance are good, a resist pattern forming composition for lithography comprising the compound represented by the formula (2) can give a good resist pattern shape.

Furthermore, even in the case of a substrate having a step (particularly, a minute space or a hole pattern or the like) at a relatively low molecular weight and low viscosity, it is easy to increase the flatness of the film while uniformly filling the corners of the step, The lower layer film forming composition for lithography used has favorable buried and planarized characteristics. In addition, since it is a compound having a relatively high carbon concentration, high etching resistance can also be imparted.

In addition, since the aromatic densities are high, the refractive index is high and coloration is suppressed even by a wide range of heat treatments from a low temperature to a high temperature. Among them, a compound having quaternary carbon is preferable from the viewpoints of suppressing oxidative decomposition of a compound, suppressing coloration, and improving heat resistance and solvent solubility. Examples of the optical component include a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast enhancement lens and the like), a retardation film, a film for electromagnetic wave shielding, A solder resist for a flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

The compound represented by the formula (2) is more preferably a compound represented by the following formula (2-1) from the viewpoints of easiness of crosslinking and solubility in an organic solvent.

(110)

(2-1)

In formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A are the same as those described in formula (2).

R ^3A is a straight chain, branched or cyclic alkyl group of 1 to 30 carbon atoms which may have a substituent, an aryl group of 6 to 30 carbon atoms which may have a substituent, an alkenyl group of 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol group, and they may be the same or different in the same naphthalene ring or benzene ring. At least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms,

R ^4A are each independently a hydrogen atom,

m ^6A are each independently an integer of 0 to 5;

When the compound represented by the formula (2-1) is used as a film forming composition for lithography for alkali development positive resists or organic development negative resists, at least one of R ^4A is an acid dissociable group. On the other hand, at least one of R ^4A dog When the formula (2-1) using the compound represented by, as an alkali developing negative resist lithographic film forming composition for the lower layer film as a lithographic film forming composition or the optical part forming composition Is a hydrogen atom.

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

(111)

(2a)

In the formula (2a), X ^A , R ^0A to R ^2A , m ^2A and n ^A are the same as those described in the formula (2).

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

(112)

(2b)

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

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

(113)

(2c)

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

The compound represented by the formula (2) is preferably a compound represented by the following formulas (BisN-1) to (BisN-4), (XBisN-1) to (XBisN-3) from the viewpoint of solubility in a further organic solvent .

(114)

(BisN-1)

(115)

(BisN-2)

≪ EMI ID =

(BisN-3)

(117)

(BisN-4)

(118)

(XBisN-1)

(119)

(XBisN-2)

(120)

(XBisN-3)

Of the above formulas (BisN-1) to (BisN-4) and (XBisN-1) to (XBisN-3), R ^3A and R ^4A are the same as those described in formula (2-1). Provided that at least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms.

[Process for producing the compound represented by the formula (2)

The compound represented by the formula (2) in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis method thereof is not particularly limited.

For example, a polyphenol compound is obtained by subjecting a phenol, a naphthol and a corresponding aldehyde or ketone under polycondensation under an acid catalyst, and subsequently introducing an allyl group into at least one phenolic hydroxyl group of the polyphenol compound And then, by heating, it is possible to obtain a Clagen transition. Further, if necessary, it may be carried out under pressure.

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

Examples of the naphthols include, but are not limited to, naphthol, methylnaphthol, methoxynaphthol, naphthalenediol, and the like. Among them, from the viewpoint of easily forming a xanthene structure, Is preferably used.

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

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethyl But are not limited to, benzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthalaldehyde, anthracene carbaldehyde, phenanthrenecarbaldehyde, pyrencarboaldehyde, furfural and the like. These may be used singly or in combination of two or more. Among them, from the viewpoint of imparting high heat resistance, it is preferable to use at least one of benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, It is preferable to use aldehyde, anthracene carbaldehyde, phenanthrenecarboaldehyde, pyrenecarboaldehyde and furfural. From the viewpoint of improving the etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethyl Those using benzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthalaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural It is more preferable.

The acid catalyst to be used in the reaction can be appropriately selected from known ones and is not particularly limited. Examples of the acid catalyst include an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; Organic acids such as oxalic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; Tungstic acid, tungstic acid, silicomolybdic acid or phosphomolybdic acid. Of these, hydrochloric acid or sulfuric acid is preferably used from the viewpoint of ease of production and ease of handling. As for the acid catalyst, one species may be used alone, or two or more species may be used in combination.

In the reaction, a reaction solvent may be used. Examples of the reaction solvent include, but are not limited to, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof, as long as the reaction with the aldehyde to be used proceeds with the naphthol have. The amount of the reaction solvent is not particularly limited and is, for example, in the range of 0 to 2,000 parts by mass based on 100 parts by mass of the reaction raw material.

The reaction temperature is not particularly limited and may be appropriately selected depending on the reactivity of the reaction raw material, but is preferably in the range of 10 to 200 ° C. From the viewpoint of selectively synthesizing the compound represented by the formula (2) in the present embodiment, the temperature is preferably low, more preferably 10 to 60 ° C.

The reaction method is not particularly limited, and for example, there can be mentioned a method in which aldehydes or ketones such as naphthols or ketones or catalysts are charged in a batch, or a method in which naphthols or aldehydes are added dropwise in the presence of a catalyst. After completion of the polycondensation reaction, in order to remove unreacted raw materials, catalysts, and the like present in the system, the temperature of the reaction kettle may be raised to 130 to 230 ° C and volatile components may be removed at about 1 to 50 mmHg.

The amount of the raw material is not particularly limited. For example, an amount of 2 mol to excess amount of naphthol or the like and 0.001 to 1 mol of an acid catalyst per 1 mol of the aldehyde is used, and 20 Min to 100 hours.

After completion of the reaction, the target product is isolated by a known method. The isolation method of the object is not particularly limited, and for example, the reaction solution is concentrated, pure water is added to precipitate a reaction product, the reaction product is cooled to room temperature, separated by filtration, , Followed by separation and purification from a by-product by a column chromatography, followed by solvent evaporation, filtration and drying to isolate the target compound.

A method of introducing an allyl group into at least one phenolic hydroxyl group of a polyphenol compound is also known.

For example, an allyl group may be introduced into at least one phenolic hydroxyl group of the compound as follows.

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

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

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

Thereafter, by heating, the allyl group introduced into the phenolic hydroxyl group can be transferred by the Clagen transition.

[Resin obtained by using the compound represented by the formula (2) as a monomer]

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

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

(121)

(4)

In the formula (4), L represents a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond.

R ^0A , R ^1A , R ^2A , m ^2A , n ^A , q ^A and X ^A are the same as those in formula (2)

When n ^A is an integer of 2 or more, the structural formulas within n ^A [] may be the same or different, and at least one of m ^2A is an integer of 2 to 6 or at least 2 m ^2A is an integer of 1 to 6 , At least one of R ^2A is a hydroxyl group, and at least one is an alkenyl group having 2 to 30 carbon atoms.

[Process for producing a resin obtained by using a compound represented by the formula (2) as a monomer]

The resin in the present embodiment is obtained by reacting the compound represented by the formula (2) with a compound having a crosslinking reactivity. As the compound having a crosslinking reactivity, any known compound can be used as long as it can oligomerize or polymerize the compound represented by the formula (2). Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates and unsaturated hydrocarbon group-containing compounds Do not.

Specific examples of the resin having the structure represented by the formula (4) include, for example, by condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone, which is a crosslinkable compound, And novolac resins.

Examples of the aldehyde used in the novolakization of the compound represented by the formula (2) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde Benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, hydroxymethylbenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, But are not particularly limited to these. Examples of the ketone include the above-mentioned ketones. Of these, formaldehyde is more preferable. On the other hand, these aldehydes and / or ketones may be used singly or in combination of two or more kinds. The amount of the aldehyde and / or ketone to be used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per 1 mole of the compound represented by the formula (2).

In the condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone, an acid catalyst may be used. The acid catalyst to be used here can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known and include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; But are not limited to, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, Organic acids such as sulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; But are not limited to, Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride, and solid acids such as silicotungstic acid, tungstic acid, silicomolybdic acid or phosphomolybdic acid. Of these, organic acids or solid acids are preferable from a viewpoint of production, and hydrochloric acid or sulfuric acid is preferable from the viewpoint of production easiness such as easy availability and ease of handling. On the other hand, 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 to be used can be suitably set according to the kinds of raw materials and catalyst to be used and furthermore the reaction conditions, and is not particularly limited, but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material. However, it is preferable to use a compound selected from the group consisting of indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, In the case of the copolymerization reaction with a compound having a non-conjugated double bond such as vinyl norborna-2-ene,? -Pinene,? -Pinene and limonene, an aldehyde is not necessarily required.

In the condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone, a reaction solvent may be used. The reaction solvent in the polycondensation is not particularly limited and may be appropriately selected from known ones. Examples of the solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, Mixed solvents, and the like. On the other hand, one solvent may be used alone, or two or more solvents may be used in combination.

The amount of these solvents to be used can be suitably set according to the type of raw material and catalyst to be used, furthermore, reaction conditions, etc., and is not particularly limited, but is preferably in the range of 0 to 2,000 parts by mass based on 100 parts by mass of the reaction raw material. Further, the reaction temperature can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 占 폚. On the other hand, as the reaction method, a known method can be appropriately selected and used. Without particular limitation, a method of collectively introducing the compound represented by the formula (2), the aldehyde and / or the ketone and the catalyst, 2) or an aldehyde and / or a ketone is added dropwise in the presence of a catalyst.

After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to the conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts existing in the system, by employing a general method such as raising the temperature of the reaction pot to 130 to 230 ° C and removing volatile components at about 1 to 50 mmHg, The novolak resin can be isolated.

Here, the resin having the structure represented by the formula (4) may be a homopolymer of the compound represented by the formula (2), or may be a copolymer with other phenols. Examples of the copolymerizable phenol include phenol, cresol, dimethyl phenol, trimethyl phenol, butyl phenol, phenyl phenol, diphenyl phenol, naphthyl phenol, resorcinol, methyl resorcinol, catechol, , Methoxyphenol, methoxyphenol, propylphenol, pyrogallol, thymol and the like, but they are not particularly limited thereto.

In addition to the above-mentioned other phenols, the resin having the structure represented by the formula (4) may be a copolymer obtained by copolymerizing with a polymerizable monomer. Examples of such copolymerizable monomers include monomers such as naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, But are not limited to, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, novornadiene, vinylnononane, pinene, limonene, and the like. On the other hand, the resin having the structure represented by the formula (4) may be a copolymer of two or more atoms (for example, a two to four member system) of the compound represented by the formula (2) Even if a copolymer of two or more members (for example, a two to four member system) of the compound represented by the formula (2) and the above-described copolymerizable monomer is used, the compound represented by the formula (2) (For example, a 3 to 4 member system) copolymer with one copolymerizable monomer may be used.

On the other hand, the molecular weight of the resin having the structure represented by the formula (4) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, more preferably 750 to 20,000. The resin having the structure represented by the above formula (4) preferably has a degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of from 1.2 to 7, in view of increasing the crosslinking efficiency and suppressing the volatile components in the baking Is preferably within the range. On the other hand, the Mw and Mn can be obtained by the methods described in Examples described later.

The resin having the structure represented by the formula (4) preferably has a high solubility in a solvent from the viewpoint that the application of the wet process becomes easier. More specifically, when 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) are used as a solvent, the solubility in the solvent is preferably 10 mass% or more. Here, the solubility in PGME and / or PGMEA is defined as " mass of resin / (mass of resin + mass of solvent) x 100 (mass%) ". For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA is " 10 mass% or more ", and when it is not dissolved, it is less than 10 mass%.

[Method for purifying compound and / or resin]

The method of purifying a compound and / or a resin in the present embodiment is a method of purifying at least one of the compound represented by the formula (0) or the resin obtained by using the compound represented by the formula (0) as a monomer, The resin obtained by using the compound represented by the formula (1), the resin obtained by using the compound represented by the formula (1) as a monomer, the compound represented by the formula (2), and the compound represented by the formula (2) A step of dissolving at least one selected from the resins obtained in a solvent to obtain a solution S and a step of bringing the resulting solution S into contact with an aqueous acid solution to extract the compound and / A first extraction step), and the solvent used in the step of obtaining the solution (S) includes a solvent which does not optionally mix with water.

In the first extraction step, the resin is preferably a resin obtained by a reaction between the compound represented by the formula (1) and / or the compound represented by the formula (2) and a compound having a crosslinking 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 the resin having the above-described specific structure can be reduced.

More specifically, in the purification method of the present embodiment, the compound (s) and / or the resin are dissolved in an organic solvent which is not optionally miscible with water to obtain a solution (S) So that the extraction treatment can be performed. Thus, after the metal component contained in the solution (S) is transferred to the aqueous phase, the organic phase and the aqueous phase are separated to obtain a compound and / or a resin having a reduced metal content.

The compound and / or the resin used in the purification method of the present embodiment may be used alone or in combination of two or more. The compound or resin may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers, and the like.

The solvent which is not optionally miscible with water used in the purification method of the present embodiment is not particularly limited but is preferably an organic solvent that can be safely applied to a semiconductor manufacturing process and specifically includes water Is an organic solvent having a solubility of less than 30%, more preferably less than 20%, and still more preferably less than 10%. The amount of the organic solvent to be used is preferably 1 to 100 times the total amount of the compound and the resin to be used.

Specific examples of the solvent that does not optionally mix with water include, but are not limited to, ethers such as diethyl ether and diisopropyl ether; Esters such as methyl acetate, ethyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone and the like Ketones; Glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; Aromatic hydrocarbons such as toluene and xylene; And halogenated hydrocarbons such as methylene chloride and chloroform. Among them, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methylisobutylketone, propylene glycol monomethyl ether acetate and ethyl acetate are preferable, and methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol Monomethyl ether acetate is more preferable, and methyl isobutyl ketone and ethyl acetate are still more preferable. Methyl isobutyl ketone, ethyl acetate and the like are industrially removed by drying or by evaporation of the solvent industrially in view of the relatively high saturation solubility of the above compound and the resin containing the compound as a constituent component The load in the process can be reduced. These solvents may be used alone or in admixture of two or more kinds.

The acidic aqueous solution used in the purification method of the present embodiment is appropriately selected from aqueous solutions in which generally known organic compounds or inorganic compounds are dissolved in water. Examples of the acidic aqueous solution include, but are not limited to, aqueous solutions of inorganic acids in which inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are dissolved in water; An organic acid aqueous solution prepared by dissolving an organic acid such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, maleic acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenol sulfonic acid, p- toluenesulfonic acid, trifluoroacetic acid, . These acidic aqueous solutions may be used alone or in combination of two or more. Among these acidic aqueous solutions, at least one inorganic acid aqueous solution selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or an aqueous solution of at least one inorganic acid selected from acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, , Phenol sulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid, and an aqueous solution of sulfuric acid, nitric acid, and an aqueous solution of carboxylic acid such as acetic acid, oxalic acid, tartaric acid, More preferred are aqueous solutions of sulfuric acid, oxalic acid, tartaric acid and citric acid, and still more preferred are aqueous solutions of oxalic acid. It is believed that the polyvalent carboxylic acid such as oxalic acid, tartaric acid, and citric acid is coordinated with the metal ion and a chelating effect is generated, so that the metal is more effectively removed. It is preferable to use water having a small metal content, for example, ion-exchanged water, etc., in accordance 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 or the resin. The pH of the acidic aqueous solution is usually about 0 to 5, and preferably about 0 to 3.

The amount of the acidic aqueous solution to be used in the purification method of the present embodiment is not particularly limited, but from the viewpoint of reducing the number of times of extraction for metal removal and from the viewpoint of ensuring operability in consideration of the total liquid amount, desirable. From the above viewpoint, the amount of the acidic aqueous solution to be used is preferably 10 to 200 mass%, more preferably 20 to 100 mass%, based on 100 mass% of the solution (S).

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

In the purification method of the present embodiment, it is preferable that the solution (S) further comprises an organic solvent optionally miscible with water. When the solution (S) contains an organic solvent optionally miscible with water, it is possible to increase the amount of the compound and / or the resin introduced, and to improve the liquid-splitting property and to carry out the purification with a high pot efficiency have. The method of adding an organic solvent optionally mixed with water is not particularly limited, and examples thereof include a method of adding the solution to a solution containing an organic solvent in advance, a method of previously adding the solution to water or an acidic aqueous solution, Or a method in which water or an acidic aqueous solution is contacted and then added. Of these, from the viewpoint of ease of operation and control of the amount of the operation, a method of adding the solution to a solution containing an organic solvent in advance is preferable.

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

Specific examples of the organic solvent optionally mixed with water used in the purification method of the present embodiment include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; Alcohols such as methanol, ethanol and isopropanol; Ketones such as acetone and N-methylpyrrolidone; Aliphatic hydrocarbons such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether. Among these, N-methylpyrrolidone and propylene glycol monomethyl ether are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable. These solvents may be used alone or in combination of two or more.

The temperature at which extraction treatment is carried out is usually 20 to 90 ° C, preferably 30 to 80 ° C. The extraction operation is carried out, for example, by mixing well by stirring or the like, and then allowing to stand. As a result, the metal component contained in the solution (S) migrates 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 can be suppressed.

The mixed solution is separated into a solution phase containing a compound and / or a resin and a solvent and a water phase by standing, so that the solution phase is recovered by decantation or the like. The time for which the solution is allowed to stand is not particularly limited, but from the viewpoint of better separation of the solution phase containing the solvent and the aqueous phase, it is preferable to adjust the time for which the solution is allowed to stand. Normally, the standing time is at least 1 minute, preferably at least 10 minutes, and more preferably at least 30 minutes. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, setting, and separation a plurality of times.

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

It is preferable that the water used herein is water having a small metal content, for example, ion-exchanged water, etc., in accordance with 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, setting, and separation a plurality of times. Conditions such as the ratio of use in the extraction treatment, temperature, and time are not particularly limited, but may be the same as in the case of the above-mentioned contact treatment with the acidic aqueous solution.

The water that can be incorporated into the solution thus obtained and / or the solution containing the resin and the solvent can be easily removed by carrying out an operation such as distillation under reduced pressure. If necessary, a solvent may be added to the solution to adjust the concentration of the compound and / or the resin to an arbitrary concentration.

The method of isolating a compound and / or a resin from a solution containing the obtained compound and / or resin and a solvent is not particularly limited and may be carried out by a known method such as removal under reduced pressure, separation by re-precipitation, . If necessary, known processes such as a concentration operation, a filtration operation, a centrifugation operation, and a drying operation can be performed.

[Composition]

The composition in the present embodiment is a resin obtained by using the compound represented by the formula (0) and the compound represented by the formula (0) as a monomer, more specifically, the compound represented by the formula (1) A resin, a solvent, an acid generator, a cross-linking agent, an ultraviolet absorber, an ultraviolet absorber, or the like obtained by using a resin obtained by using a compound represented by the formula (1) as a monomer, a compound represented by the formula (2) A crosslinking accelerator, a radical polymerization initiator, and the like.

The composition of the present embodiment may be a film forming composition for lithography or an optical component forming composition.

[Film forming composition for lithography for chemically amplified resist application]

(Hereinafter also referred to as a " resist composition ") for use in a chemically amplified resist according to the embodiment of the present invention is a composition comprising a compound represented by the formula (0) and a compound represented by the formula (1), a resin obtained by using the compound represented by the formula (1) as a monomer, a compound represented by the formula (2), and a resin obtained by using the compound represented by the formula (2) And a resin obtained by using a compound represented by the following formula as a monomer.

It is preferable that the composition (resist composition) in the present embodiment further contains a solvent. Examples of the solvent include, but are not limited to, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate and ethylene glycol mono-n- Monoalkyl ether acetates; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate; Aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate and ethyl propionate; Methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy- Other esters such as 3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); Amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as? -lactone, and the like, but they are not particularly limited to these. These solvents may be used alone or in combination of two or more.

The solvent used in this embodiment is preferably a safe solvent and more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, And more preferably at least one species 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 it is preferably from 1 to 80 mass% of the solid component and from 20 to 99 mass% of the solvent, based on 100 mass% of the total mass of the solvent and the amount of the solid component , More preferably from 1 to 50 mass% of a solid component and from 50 to 99 mass% of a solvent, more preferably from 2 to 40 mass% of a solid component and from 60 to 98 mass% of a solvent, Mass% and the solvent is 90 to 98 mass%.

The composition (resist composition) of the present embodiment contains at least one kind selected from the group consisting of the acid generator (C), the crosslinking agent (G), the acid diffusion controlling agent (E) May be further contained. In the present specification, the term " solid component " refers to a component other than a solvent.

As the acid generator (C), the cross-linking agent (G), the acid diffusion controller (E) and the other components (F), publicly known ones can be used. 024778 is preferable.

[Compounding ratio of each component]

In the resist composition of the present embodiment, the content of the compound and / or resin used as the resist base material is not particularly limited, but the total mass of the solid component (resist substrate, acid generator (C), crosslinking agent (G) More preferably from 55 to 90% by mass, more preferably from 50 to 90% by mass of the total amount of solid components including optional components such as the control agent (E) and other components (F) More preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass. When the content of the compound and / or resin used as the resist base material is in the above range, the resolution is further improved and the line edge roughness (LER) tends to be further reduced.

On the other hand, when both the compound and the resin are contained as the resist base material, the above content is the total amount of both components.

[Other components (F)]

The resist composition according to the present embodiment may contain a component other than the resist substrate, the acid generator (C), the crosslinking agent (G) and the acid diffusion controlling agent (E), if necessary, A thermosetting resin, a photo-curable resin, a photo-curing resin, a photo-curing resin, a photo-curing resin, a photo-curing resin One or more kinds of additives such as a coloring agent, a dye, a pigment, a thickener, a lubricant, a defoaming agent, a leveling agent, an ultraviolet absorber, a surfactant, a colorant and a nonionic surfactant. On the other hand, in the present specification, the other component (F) is also referred to as optional component (F).

The acid generator (C), the crosslinking agent (G), the acid diffusion control agent (E), and the optional component (F) are used in the resist composition of the present embodiment. The content (mass% based on solids) of the component (A) / acid generator (C) / crosslinking agent (G) / acid diffusion controller (E) / optional component (F)

Preferably 50 to 99.4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49/0 to 49,

More preferably 55 to 90/1 to 40 / 0.5 to 40 / 0.01 to 10/0 to 5,

More preferably 60 to 80/3 to 30/1 to 30 / 0.01 to 5/0 to 1,

And particularly preferably 60 to 70/10 to 25/2 to 20/0 0.01 to 3/0.

The blending ratio of each component is selected from each range so that the total sum is 100% by mass. When the mixing ratio of each component is in the above range, performance such as sensitivity, resolution, developability tends to be excellent.

The resist composition of the present embodiment is usually prepared by dissolving each component in a solvent to prepare a homogeneous solution at the time of use and then filtering it with a filter having a pore diameter of about 0.2 m if necessary.

The resist composition of the present embodiment may contain other resins than the resin of this embodiment within the range not hindering the object of the present invention. The other resin is not particularly limited and includes, for example, novolac resins, polyvinyl phenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol, or vinylphenol as monomer units Or a derivative thereof, and the like. The content of the other resin is not particularly limited and is appropriately adjusted according to the kind of the component (A) to be used. It is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, More preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.

[Physical properties of resist composition]

By using the resist composition of the present embodiment, an amorphous film can be formed by spin coating. Further, the resist composition of the present embodiment can be applied to a general semiconductor manufacturing process. Depending on the kind of the resin obtained by using the compound represented by the formula (1) and / or the formula (2), and the type of the developer obtained by using these as the monomer and / or the type of the developer to be used, any one of the positive resist pattern and the negative resist pattern Can be made.

In the case of the positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition of the present embodiment with respect to the developer at 23 캜 is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å, More preferably 0.0005 to 5 占 sec. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developer and tends to be easily made into a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because, depending on the change in the solubility before and after exposure of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as a constituent component, the exposure part dissolving in the developing solution, It is presumed that the contrast of the interface of the unexposed portion increases. It also shows the reduction of LER and the effect of 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 with respect to the developer at 23 캜 is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is used for a developing solution, and is suitable for a resist. When the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably because the surface portions of the microparticles of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as the constituent component are dissolved and the LER is reduced. It also shows the effect of reducing defects.

The dissolution rate can be determined by immersing the amorphous film in a developing solution at 23 占 폚 for a predetermined time and measuring the film thickness before and after the immersion by a known method such as an ellipsometer or a QCM method.

In the case of a positive resist pattern, the resist composition of the present embodiment is dissolved in a developing solution at 23 占 폚 in a KrF excimer laser of an amorphous film formed by spin coating, exposed by radiation such as extreme ultraviolet ray, electron beam or X- The speed is preferably 10 angstroms / sec or more. When the dissolution rate is 10 Å / sec or more, it is used for a developing solution, and is suitable for a resist. When the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably because the surface portions of the microparticles of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as the constituent component are dissolved and the LER is reduced. It also shows the effect of reducing defects.

In the case of a negative resist pattern, the resist composition of the present embodiment is dissolved in a developing solution at 23 deg. C in a KrF excimer laser of an amorphous film formed by spin coating, exposed by radiation such as extreme ultraviolet ray, electron beam or X- The speed is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and still more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developer and tends to be easily made into a resist. In addition, when the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because, depending on the change in the solubility before and after exposure of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing this compound as a component, It is presumed that the contrast of the interface of the exposed portion increases. It also shows the reduction of LER and the effect of reducing defects.

[Film forming composition for lithography for non-chemically amplified resist application]

The component (A) to be contained in the film forming composition for lithography for a non-chemically amplified resist application (hereinafter also referred to as " radiation-sensitive composition ") of the present embodiment can be used in combination with a diazonaphthoquinone photoactive compound (B) And is useful as a substrate for a positive type resist which is a phosphorus compound used in a developer by irradiation with a g line, h line, i line, KrF excimer laser, ArF excimer laser, extreme ultraviolet ray, electron beam or X ray. The properties of the component (A) are not largely changed by the g line, the h line, the i line, the KrF excimer laser, the ArF excimer laser, the extreme ultraviolet ray, the electron beam or the X ray. However, the diazonaphthoquinone photoactive compound (B) is changed to a compound to be used, it becomes possible to form a resist pattern by a developing process.

Since the component (A) contained in the radiation sensitive composition of the present embodiment is a compound having a relatively low molecular weight, the obtained resist pattern has a very low roughness. In the formula (1), at least one group selected from the group consisting of R ⁰ to R ⁵ is preferably a group containing an iodine atom. In the formula (2), R ^0A , R ^{1 A} and R ^{2 A} Is a group containing at least one iodine atom. When the component (A) having a group containing an iodine atom is applied, the radiation sensitive composition of the present embodiment increases the absorption ability for radiation such as electron beam, extreme ultraviolet (EUV), and X-ray, It is preferable to increase the height.

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

The crystallization calorific value 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. The (crystallization temperature) - (glass transition temperature) is preferably 70 ° C or more, more preferably 80 ° C or more, still more preferably 100 ° C or more, particularly preferably 130 ° C or more. When the crystallization calorific value is less than 20 J / g or (crystallization temperature) - (glass transition temperature) is within the above range, the amorphous film is easily formed by spin coating the radiation sensitive composition and the film- And there is a tendency to improve the resolution.

In the present embodiment, the crystallization heat generation amount, crystallization temperature and glass transition temperature can be obtained by differential scanning calorimetry using DSC / TA-50WS manufactured by Shimadzu Corporation. Approximately 10 mg of the sample is placed in a container made of aluminum and heated in a nitrogen gas stream (50 mL / min) to a melting point or more at a heating rate of 20 캜 / minute. After quenching, the temperature is raised again to the melting point or higher in a nitrogen gas stream (30 mL / min) at a heating rate of 20 DEG C / min. After quenching again, the temperature is raised again to 400 DEG C in a nitrogen gas stream (30 mL / min) at a heating rate of 20 DEG C / min. The temperature of the glass transition temperature (Tg) and the temperature of the exothermic peak appearing thereafter are set as the crystallization temperature at the midpoint (the point where the specific heat is changed in half) of the step of the baseline changed to stick. The calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline to obtain the calorific calorific value.

The component (A) contained in the radiation sensitive composition of the present embodiment is preferably at most 100 ° C, preferably at most 120 ° C, more preferably at most 130 ° C, more preferably at most 140 ° C, It is preferable that the sublimation property is lower than 150 deg. The reason why the sublimation property is low is that in the 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, further preferably 1% Or less, particularly preferably 0.1% or less. By lowering the sublimation property, it is possible to prevent the exposure apparatus from being contaminated by the outgassing during exposure. A low roughness and a good pattern shape can be obtained.

The component (A) to be contained in the radiation sensitive composition of the present embodiment is at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone Preferably 1% by mass or more, at 23 占 폚, in a solvent which is selected from the group consisting of ethyl acetate, 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate and which exhibits the highest solubility for component (A) Or more, more preferably 5 mass% or more, and further preferably 10 mass% or more. Particularly preferably, the solvent is selected from the group consisting of PGMEA, PGME and CHN, and is further added to a solvent which exhibits the highest solubility in the resist substrate (A) at 23 占 폚, 20% by mass or more, particularly preferably PGMEA At 20 占 폚 or more at 23 占 폚. By satisfying the above condition, it is easy to use in the semiconductor manufacturing process in the actual production.

[Diazonaphthoquinone photoactive compound (B)]

The diazonaphthoquinone photoactive compound (B) contained in the radiation sensitive composition of the present embodiment is a diazonaphthoquinone substance including a polymerizable and nonpolymeric diazonaphthoquinone photoactive compound, and generally, a positive resist composition , Any one or more of them may be arbitrarily selected and used as long as they are used as a photosensitive component (photosensitizer) without particular limitation.

As the component (B), a compound obtained by reacting a naphthoquinone diazide sulfonic acid chloride, benzoquinone diazide sulfonic acid chloride or the like with a low molecular compound having a functional group capable of condensation reaction with these acid chloride or a polymer compound is preferable. Here, the functional group capable of condensation with an acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, but hydroxyl groups are especially preferred. The compound capable of condensation with an acid chloride including a hydroxyl group is not particularly limited and includes, for example, hydroquinone, resorcin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'- Hydroxybenzophenones such as tetrahydroxybenzophenone, 2,2 ', 3,4,6'-pentahydroxybenzophenone, and the like; Hydroxyphenylalkanes such as bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane and bis (2,4-dihydroxyphenyl) propane; 4,4 ', 3 ", 4" -tetrahydroxy-3,5,3', 5'-tetramethyltriphenylmethane, 4,4 ' , And 5,3 ', 5'-tetramethyltriphenylmethane, and the like.

Examples of the acid chloride such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride include 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide sulfonic acid chloride, Toquinonediazide-4-sulfonyl chloride, and the like.

The radiation sensitive composition of the present embodiment can be obtained by, for example, dissolving each component in a solvent to prepare a homogeneous solution at the time of use, and then, if necessary, filtering with a filter having a pore diameter of about 0.2 m It is preferable to prepare them.

[Characteristics of radiation-sensitive composition]

The amorphous film can be formed by spin coating using the radiation sensitive composition of this embodiment. Further, the radiation sensitive composition of the present embodiment can be applied to a general semiconductor manufacturing process. Depending on the type of the developing solution to be used, any one of the positive resist pattern and the negative resist pattern can be separately formed.

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 the developer at 23 캜 is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec More preferably 0.0005 to 5 ANGSTROM / sec. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developer and tends to be easily made into a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because, depending on the change in the solubility before and after exposure of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as a constituent component, the exposure part dissolving in the developing solution, It is presumed that the contrast of the interface of the unexposed portion increases. It also shows the reduction of LER and the effect of reducing defects.

In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin coating of the radiation sensitive composition of the present embodiment in a developer at 23 캜 is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is used in a developing solution, and is suitable for a resist. When the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably because the surface portions of the microparticles of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as the constituent component are dissolved and the LER is reduced. It also shows the effect of reducing defects.

The dissolution rate can be determined by immersing the amorphous film in a developing solution at 23 占 폚 for a predetermined time and measuring the film thickness before and after the immersion by a known method such as an ellipsometer or a QCM method.

In the case of the positive resist pattern, the radiation sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet ray, electron beam or X-ray of an amorphous film formed by spin coating, , The dissolution rate of the exposed portion to the developer at 23 캜 is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, and further preferably 100 to 1000 Å / sec. When the dissolution rate is 10 Å / sec or more, it is used for a developing solution, and is suitable for a resist. When the dissolution rate is 10,000 Å / sec or less, the resolution may be improved. This is presumably because the surface portions of the microparticles of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as the constituent component are dissolved and the LER is reduced. It also shows the effect of reducing defects.

In the case of the negative type resist pattern, the radiation sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet ray, electron beam or X-ray of an amorphous film formed by spin coating, or after heating at 20 to 500 ° C The dissolution rate of the exposed portion to the developer at 23 캜 is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and still more preferably 0.0005 to 5 Å. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developer and tends to be easily made into a resist. In addition, when the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because, depending on the change in the solubility before and after exposure of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing this compound as a component, It is presumed that the contrast of the interface of the exposed portion increases. It also shows the reduction of LER and the effect of reducing defects.

[Compounding ratio of each component]

In the radiation sensitive composition of the present embodiment, the content of the component (A) is not particularly limited so long as the total mass of the solid component (component (A), diazonaphthoquinone photoactive compound (B) Is preferably from 1 to 99% by mass, more preferably from 5 to 95% by mass, still more preferably from 10 to 90% by mass, and particularly preferably from 25 to 75% by mass, based on the total amount of the solid components %to be. When the content of the component (A) is within the above range, the radiation sensitive composition of the present embodiment tends to obtain a pattern with a high sensitivity and a small roughness.

The content of the diazonaphthoquinone photoactive compound (B) in the radiation sensitive composition of the present embodiment is preferably such that the total mass of the solid component (component (A), diazonaphthoquinone photoactive compound (B) and other components (D) Is preferably from 1 to 99% by mass, more preferably from 5 to 95% by mass, further preferably from 10 to 90% by mass, and particularly preferably from 5 to 95% by mass, relative to the total amount of solid components optionally used Is 25 to 75% by mass. When the content of the diazonaphthoquinone photoactive compound (B) is within the above range, the radiation sensitive composition of the present embodiment tends to obtain a pattern with high sensitivity and small roughness.

[Other components (D)]

The radiation sensitive composition of the present embodiment may contain, as necessary, components other than the component (A) and the diazonaphthoquinone photoactive compound (B), such as an acid generator, a crosslinking agent, A heat and / or light curing catalyst, a polymerization inhibitor, a flame retardant, a filler, a coupling agent, a thermosetting resin, a heat stabilizer, an acid diffusion controlling agent, a dissolution accelerator, a solubilizer, a sensitizer, a surfactant, It is possible to add one or more kinds of additives such as a photo-curing resin, a dye, a pigment, a thickener, a lubricant, a defoaming agent, a leveling agent, an ultraviolet absorber, a surfactant, a colorant and a nonionic surfactant. In the present specification, the other component (D) is also referred to as an optional component (D).

In the radiation sensitive composition of the present embodiment, the compounding ratio (component (A) / diazonaphthoquinone photoactive compound (B) / optional component (D)) of each component is,

Preferably 1 to 99/99 to 1/0 to 98,

More preferably 5 to 95/95 to 5/0 to 49,

More preferably 10 to 90/90 to 10/0 to 10,

Still more preferably 20 to 80/80 to 20/0 to 5,

And particularly preferably 25 to 75/75 to 25/0.

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

The radiation sensitive composition of the present embodiment may contain other resins insofar as the object of the present invention is not impaired. Examples of such other resins include novolak resins, polyvinyl phenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, polymers containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units, or derivatives thereof . The amount of these resins to be blended is appropriately controlled depending on the kind of the component (A) to be used, and is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and most preferably 10 parts by mass or less, Is 5 parts by mass or less, particularly preferably 0 parts by mass.

[Method of forming resist pattern]

The method of forming a resist pattern in this embodiment is a method of forming a photoresist layer on a substrate by using the resist composition or the radiation sensitive composition of the present embodiment described above, And a step of irradiating radiation and performing development. More particularly, the present invention relates to a method of forming a resist pattern, which comprises the steps of forming a resist film on a substrate using the resist composition or the radiation sensitive composition of the present invention described above, exposing the formed resist film, Process. The resist pattern in the present embodiment may be formed as an upper layer resist in a multilayer process.

The method for forming the resist pattern is not particularly limited, and for example, the following methods can be used. First, a resist composition or a radiation-sensitive composition is applied onto a conventionally known substrate by a coating means such as spin coating, soft coating or roll coating to form a resist film. The conventionally known substrate is not particularly limited and includes, for example, a substrate for electronic parts and a substrate having a predetermined wiring pattern formed thereon. More specifically, examples thereof include substrates made of metal such as silicon wafers, copper, chromium, iron and aluminum, and glass substrates. Examples of the material of the wiring pattern include copper, aluminum, nickel, gold and the like. In addition, if necessary, an inorganic and / or organic film may be provided on the above-described substrate. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) can be mentioned. The organic film may be an organic anti-reflection film (organic BARC). The substrate may be subjected to surface treatment with hexamethyldisilazane or the like.

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

Subsequently, the exposed resist film is developed with a developing solution to form a predetermined resist pattern. As the developer, a solvent having a solubility parameter (SP value) close to that of a resin obtained by using a compound represented by the formula (1) or (2) or a compound represented by the formula (1) or (2) It is preferable to use a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent or an ether solvent, a hydrocarbon solvent or an aqueous alkali solution.

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, Ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, Isophorone, propylene carbonate, and the like.

Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene Methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, lactic acid, ethyl lactate, ethyl lactate, ethyl lactate, ethyl lactate, Butyl, and propyl lactate.

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

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

Examples of the amide-based solvent include N, N-dimethyl-acetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl- - imidazolidinone, and the like.

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

A plurality of the above-mentioned solvents may be mixed, or they may be mixed with a solvent or water other than the above in a range of performance. However, from the viewpoint of sufficiently exhibiting the effects of the present invention, the water content of the developer as a whole is preferably less than 70 mass%, more preferably less than 50 mass%, more preferably less than 30 mass%, further preferably less than 10 mass% It is particularly preferable that substantially no moisture is contained. That is, the content of the organic solvent in the developer is preferably 30 mass% or more and 100 mass% or less, more preferably 50 mass% or more and 100 mass% or less, more preferably 70 mass% or more and 100 mass% or less More preferably 90% by mass or more and 100% by mass or less, still more preferably 95% by mass or more and 100% by mass or less.

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

Particularly, as the developer, at least one kind of developer selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent is preferably used as the developer in order to improve resist resolution and resist performance such as roughness A developing solution containing a solvent is preferable.

The vapor pressure of the developer is preferably 5 kPa or less at 20 캜, more preferably 3 kPa or less, and further preferably 2 kPa or less. When the vapor pressure of the developing solution is 5 kPa or less, evaporation of the developing solution 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 within the wafer surface tends to be quantified.

Examples of a specific developer having a vapor pressure of 5 kPa or less at 20 占 폚 include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone , Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone and methylisobutylketone; 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-methoxy Ester solvents such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate and propyl lactate; propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, Alcohol solvents such as alcohol and n-decanol; Glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; Glycol ether solvents 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 methoxymethyl butanol; Ether solvents such as tetrahydrofuran; Amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide; Aromatic hydrocarbon solvents such as toluene and xylene; And aliphatic hydrocarbon solvents such as octane and decane.

Examples of the specific developer having a vapor pressure of 2 kPa or less at 20 캜 include 1-octanone, 2-octanone, 1-nonanone, 2- , Ketone solvents such as cyclohexanone, methylcyclohexanone, and phenylacetone; Butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxy Ester solvents such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, and propyl lactate; alcohols such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, Based solvent; Glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; Glycol ether solvents 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 methoxymethyl butanol; Aromatic hydrocarbon solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide amide solvents and xylene; And aliphatic hydrocarbon solvents such as octane and decane.

To the developer, an appropriate amount of a surfactant may be added, if necessary. The surfactant is not particularly limited and, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. These fluorine and / or silicon surfactants include, for example, those disclosed in Japanese Patent Application Laid-Open No. S62-36663, Japanese Patent Application Laid-Open No. S61-226746, Japanese Patent Application Laid-Open No. S61-226745, Japanese Laid-Open Patent Publication No. S62-170950 , Japanese Patent Application Laid-Open Nos. S63-34540, H7-230165, H8-62834, H9-54432, H9-5988, US5405720 Surfactants described in JP-B-5360692, JP-B-5529881, JP-B-5296330, JP-A-5436098, JP-B-5576143, JP-A-5294511 and JP- It is a nonionic surfactant. The nonionic surfactant is not particularly limited, but is preferably a fluorine surfactant or a silicone surfactant.

The amount of the surfactant to be used is usually 0.001 to 5 mass%, preferably 0.005 to 2 mass%, more preferably 0.01 to 0.5 mass%, based on the whole amount of the developer.

Examples of the developing method include a method (dip method) in which the substrate is immersed in a tank filled with the developing solution for a predetermined time (a dipping method), a developing method (puddle method) in which the developing solution is raised by surface tension on the substrate surface for a predetermined time, A method of spraying a developer (spray method), a method of continuously drawing a developer while scanning a nozzle for drawing out a developer at a constant speed on a substrate rotating at a constant speed (dynamic dispensing 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 development, a step of stopping development while replacing with another solvent may be performed.

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

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

Examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols. Specific examples thereof include 1-butanol, 2-butanol, 3-methyl- 2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-pentanol, 2-butanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used. Particularly preferred monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like.

A plurality of the above components may be mixed together, or they may be mixed with other organic solvents.

The water content in the rinsing liquid is preferably 10 mass% or less, more preferably 5 mass% or less, and further preferably 3 mass% or less. When the water content in the rinsing liquid is 10 mass% or less, more excellent developing characteristics tend to be obtained.

The vapor pressure of the rinsing liquid used after development is preferably 0.05 kPa or more and 5 kPa or less at 20 캜, more preferably 0.1 kPa or more and 5 kPa or less, and further preferably 0.12 kPa or more and 3 kPa or less. When the vapor pressure of the rinsing liquid is 0.05 kPa or more and 5 kPa or less, the temperature uniformity within the wafer surface is further improved, further swelling due to infiltration of the rinsing liquid is further suppressed, and the dimensional uniformity within the wafer surface is more favorable .

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

In the rinsing process, the developed wafer is cleaned using a rinsing liquid containing the organic solvent. The method of the rinsing treatment is not particularly limited. For example, there is a method of continuously extracting the rinsing liquid onto the substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in the rinsing liquid filled tank for a certain time A method of spraying a rinsing liquid onto the surface of a substrate (spraying method), and the like can be applied. Among them, a cleaning treatment is carried out by a spin coating method, the substrate is rotated at a rotation number of 2000 rpm to 4000 rpm after cleaning, It is preferable to remove the rinsing liquid from the substrate.

After the resist pattern is formed, etching is performed to obtain a pattern wiring substrate. The etching can be performed by a known method such as dry etching using a plasma gas and wet etching using an alkali solution, copper chloride solution, ferric chloride solution or the like.

After the resist pattern is formed, plating may be performed. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

The remaining resist pattern after etching can be peeled off with an organic solvent. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), and the like. The peeling method includes, for example, an immersion method, a spray method, and the like. 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 in the present embodiment may be formed by depositing a metal in a vacuum after forming a resist pattern, and thereafter dissolving the resist pattern in a solution, that is, by a lift-off method.

[Film forming composition for lithography for underlayer film application]

The film forming composition for lithography for use in a lower layer film in the present embodiment (hereinafter also referred to as " lower layer film forming material ") comprises a compound represented by the formula (0) and a compound represented by the formula (0) (1), a resin obtained by using the compound represented by the formula (1) as a monomer, a compound represented by the formula (2), and a resin obtained by using the compound represented by the formula (2) And a resin obtained by using a compound obtained by subjecting a compound represented by the general formula (1) as a monomer. In the present embodiment, the material is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and more preferably 50 to 100% by mass in the total mass of the solid component, , And particularly preferably 100% by mass.

The lower film forming material of the present embodiment is applicable to a wet process, and is excellent in heat resistance and etching resistance. Further, since the lower layer film forming material of this embodiment uses the above-described material, deterioration of the film at the time of high-temperature baking is suppressed, and a lower layer film excellent in etching resistance against oxygen plasma etching and the like can be formed. Furthermore, the lower layer film forming material of the present embodiment has excellent adhesion with the resist layer, and therefore, an excellent resist pattern can be obtained. On the other hand, the lower film forming material of the present embodiment may contain a known material for forming a lower layer film for lithography within the range in which the effect of the present invention is not impaired.

[menstruum]

The lower layer film forming material in this embodiment may contain a solvent. As the solvent used for the lower layer film forming material, any known one may be appropriately used as long as the above-mentioned substance is dissolved at least.

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

Of these 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 from 100 to 10,000 parts by mass, more preferably from 200 to 5,000 parts by mass, still more preferably from 200 to 5,000 parts by mass based on 100 parts by mass of the total mass of the solid component from the viewpoints of solubility and film- More preferably 1000 parts by mass.

[Crosslinking agent]

The lower layer film forming material in this embodiment may contain a crosslinking agent if necessary in view of suppressing intermixing or the like. The crosslinking agent is not particularly limited and, for example, those described in International Publication No. 2013/024779 can be used.

Specific examples of the crosslinking agent that can be used in the present embodiment include a phenol compound, an epoxy compound, a cyanate compound, an amino compound, a benzoxazine compound, an acrylate compound, a melamine compound, a guanamine compound, Urea compounds, isocyanate compounds, and azide compounds, but are not limited thereto. These crosslinking agents may be used singly or in combination of two or more kinds. Among them, a benzoxazine compound, an epoxy compound or a cyanate compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improving the etching resistance.

As the phenol compound, known ones can be used. Examples of the phenols include, in addition to phenol, alkyl phenols such as cresols and xylylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalene diols, bisphenols such as bisphenol A and bisphenol F, And polyfunctional phenol compounds such as phenol novolak and phenol aralkyl resin. Among them, an aralkyl type phenol resin is preferable in view of heat resistance and solubility.

As the epoxy compound, known epoxy compounds can be used, and those having two or more epoxy groups in one molecule are selected. Bisphenol A, bisphenol F, 3,3 ', 5,5'-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2'-biphenol, 3,3' -Tetramethyl-4,4'-dihydroxybiphenol, resorcin, naphthalene diol, and other divalent phenols such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetra Tris (2,3-epoxypropyl) isocyanurate, trimethylol methane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylol ethane triglycidyl ether, phenol (4-hydroxyphenyl) Epoxides of phenols having three or more valences such as novolak and o-cresol novolak, epoxides of cocondensation resins of dicyclopentadiene and phenols, epoxides of phenol aralkyls such as phenols and paraxylylene dihydrochloride , Biphenyl aralkyl type phenol synthesized from phenols and bischloromethylbiphenyl Epoxides of naphthol aralkyls such as epoxides of resins, naphthols and para-xylylene di-chlorides, and the like. These epoxy resins may be used alone or in combination of two or more. It is preferably a solid epoxy resin at room temperature such as an epoxy resin obtained from a phenol aralkyl group and a biphenyl aralkyl group in view of heat resistance and solubility.

As the cyanate compound, a compound having two or more cyanate groups in one molecule may be used without particular limitation. In the present embodiment, preferred examples of the cyanate compound include those having a structure in which a hydroxyl group of a compound having two or more hydroxyl groups in one molecule is substituted with a cyanate group. Further, the cyanate compound preferably has an aromatic group, and it can be suitably used that the cyanate group has a structure directly connected to an aromatic group. Examples of such cyanate compounds include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolak resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethyl bisphenol F, A novolac 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, Pentadiene aralkyl resin, alicyclic phenol, phosphorus-containing phenol and the like are substituted with a cyanate group. These cyanate compounds may be used alone or in combination of two or more. The cyanate compound may be any of monomers, oligomers and resins.

Examples of the amino compound include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether , 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'- Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy ) Benzene, 1,3- bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) 3-aminophenoxy) phenyl] (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9- (Trifluoromethyl) -4,4'-diaminobiphenyl, 4-aminophenyl, 4,4'-diaminobenzanilide, 2,2'-bis Aminobenzoate, 2- (4-aminophenyl) -6-aminobenzoxazole, and the like. Further, there can be mentioned 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, Diaminodiphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4 (Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis Bis [4- (3-aminophenoxy) phenyl] propane, 4,4'-bis (4-aminophenoxy) phenyl] propane, 2,2- Biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- Aromatic amines such as diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diamino dicyclohexylmethane, tetramethyl-diamino dicyclohexylmethane, diamino dicyclohexyl Bis (aminomethyl) tricyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4) , 6] decane, 1,3-bisaminomethylcyclohexane, and isophoronediamine; alicyclic amines such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylenetriamine and triethylenetetramine; Aliphatic amines and the like.

Examples of the benzoxazine photographic compound include P-d type benzoxazine obtained from bifunctional diamines and monofunctional phenols, F-a type benzoxazine obtained from monofunctional diamines and bifunctional phenols, and the like.

Specific examples of the melamine compound include, for example, compounds obtained by methoxymethylating 1 to 6 methylol groups of hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, or mixtures thereof, hexamethoxyethyl melamine , Hexaacyloxymethyl melamine, compounds obtained by acyloxymethylating 1 to 6 methylol groups of hexamethylol melamine, and mixtures thereof.

Specific examples of the above-mentioned guanamine compound include compounds obtained by methoxymethylating 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, tetramethylolguanamine, or a mixture thereof, tetra A compound obtained by acyloxymethylating 1 to 4 methylol groups of methoxyethylguanamine, tetraacyloxyguanamine and tetramethylolguanamine, or a mixture thereof.

Specific examples of the glycoluril compound include, for example, methoxymethylated 1 to 4 methylol groups of tetramethylolglycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, tetramethylolglycoluril, A compound or a mixture thereof, a compound obtained by acyloxymethylating 1 to 4 methylol groups of tetramethylolglycoluril, or a mixture thereof.

Specific examples of the urea compound include, for example, a compound obtained by methoxymethylating 1 to 4 methylol groups of tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea, or a mixture thereof, tetramethoxyethylurea And the like.

In the present embodiment, from the viewpoint of improving the crosslinkability, a crosslinking agent having at least one allyl group may also be used. Specific examples of the crosslinking 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 Allyl phenols such as 2,2-bis (3-allyl-4-cyanatophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-cyanatophenyl) sulfone, bis (3-allyl-4-cyanatophenyl) sulfone, bis Diallyl phthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol allyl ether and the like can be mentioned. However, It is not limited to these illustrated ones. These may be used singly or as a mixture of two or more kinds. Among them, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Allyl phenols) such as bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) .

The content of the crosslinking agent in the lower layer film forming material is not particularly limited, but is preferably 0.1 to 50 mass%, more preferably 5 to 50 mass%, and still more preferably 10 to 40 mass%, of the total mass of the solid component. to be. When the content of the crosslinking agent is within the above range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect increases, and the film formability after crosslinking tends to increase.

[Crosslinking accelerator]

As the lower layer film forming material of the present embodiment, a cross-linking accelerator for promoting cross-linking and curing reaction may be used if necessary.

Examples of the crosslinking accelerator include amines, imidazoles, organic phosphines, and Lewis acids, as long as they facilitate crosslinking and curing reactions. These crosslinking accelerators may be used singly or in combination of two or more. Of these, imidazoles or organic phosphines are preferable, and imidazoles are more preferable from the viewpoint of lowering the crosslinking temperature.

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

The content of the crosslinking accelerator is usually from 0.1 to 10 mass%, preferably from 0.1 to 5 mass%, more preferably from 0.1 to 5 mass%, from the viewpoints of control easiness and economical efficiency, 0.1 to 3% by mass.

[Radical polymerization initiator]

The lower layer film forming material of the present embodiment may contain a radical polymerization initiator if necessary. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or may be a thermal polymerization initiator that initiates radical polymerization by heat. The radical polymerization initiator may be at least one selected from the group consisting of, for example, a ketone-based photopolymerization initiator, an organic peroxide-based polymerization initiator, and an azo-based polymerization initiator.

Such a radical polymerization initiator is not particularly limited, and any conventionally used radical polymerization initiator can be suitably employed. For example, 1-hydroxycyclohexyl phenyl ketone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) 2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2- Ketone-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; But are not limited to, ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetate peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, (T-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- ) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1,1- Bis (4,4-di-t-butylperoxycyclohexyl) propane, p-menthol hydroperoxide, di T-butyl hydroperoxide, t-butyl hydroperoxide, t-butyl hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethyl butyl hydroperoxide, cumene hydroperoxide, Butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, Dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, Di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butyl) propyl peroxide, Cyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di- (3-methyl-3-methoxybutyl) peroxydicarbonate,?,? '- bis (neodecanoylperoxy) diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-tetra Methyl butyl peroxyneodecanoate, 1-cyclohexyl-1-methyl ethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxy Butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylper Oxyhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate , t Butyl peroxyisobutyrate, t-butyl peroxymaleate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t- t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butyl peroxy-m-tolyl benzoate, t-butyl peroxybenzoate , 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-hexyl peroxybenzoate, 2,5-dimethyl- Butyl peroxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2, 3-dimethyl-2,3-diphenylbutane, and other organic peroxide-based polymerization initiators.

Also, examples of the azo compounds include 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1 - [(1-cyano- Azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvalero Aziridine), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N- phenylpropionamidine) dihydrochloride, 2,2'- Azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- Azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'- Dihydro] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] di Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- Dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride Azo [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- Dihydrochloride, 2,2'-azobis [2- [1- (2-hydroxyethyl) -2-imide 2-yl] propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin- Bis [(hydroxymethyl) ethyl] propionamide], 2,2'-azobis [2-methyl-N- [1,1- Amide], 2,2'-azobis [2-methyl-N- (2- Azobis (2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2 Azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2- Methyl) propionitrile] can be used. As the radical polymerization initiator in the present embodiment, any one of these radical polymerization initiators may be used alone or in combination of two or more. Other known polymerization initiators may be further used in combination.

The content of the radical polymerization initiator may be in a stoichiometric amount, preferably 0.05 to 25% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the solid component. When the content of the radical polymerization initiator is 0.05 mass% or more, insufficient curing tends to be prevented. On the other hand, when the content of the radical polymerization initiator is 25 mass% or less, The storage stability tends to be prevented from being impaired.

[Acid generator]

The lower layer film forming material in this embodiment may contain an acid generator if necessary in view of further promoting a crosslinking reaction by heat or the like. Examples of the acid generator include those which generate an acid by thermal decomposition and generate an acid by light irradiation, but any of them can be used. As the acid generator, for example, those described in International Publication No. 2013/024779 can be used.

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

[Basic compound]

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

The basic compound serves as a chirality for the acid to prevent the acid generated from a small amount from the acid generator from proceeding the crosslinking reaction. Such a basic compound is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

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

[Other additives]

The lower layer film forming material in the present embodiment may contain other resins and / or compounds for the purpose of imparting curability by heat or light and controlling the absorbance. Such other resins and / or compounds include phenol-modified resins of naphthol resin, xylene resin naphthol-modified resin and naphthalene resin; (Meth) acrylate, dimethacrylate, trimethacrylate, tetramethacrylate, vinylnaphthalene, polyacenaphthylene and the like, phenanthrene quinone, fluorene (meth) acrylate, A resin including a heterocycle having a hetero atom such as a biphenyl ring, thiophene or indene, or a resin not containing an aromatic ring; A resin or a compound containing an alicyclic structure such as a rosin resin, a cyclodextrin, an adamantane (poly) ol, a tricyclodecane (poly) ol and a derivative thereof, and the like. Furthermore, the lower layer film forming material in this embodiment mode may contain known additives. Known additives include, but are not limited to, heat and / or light curing catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, Defoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants, and the like.

[Lower layer film for lithography and method of forming multi-layer resist pattern]

The lower layer film for lithography in this embodiment is formed from the above-described lower layer film forming material.

The resist pattern forming method of the present embodiment is a method of forming a resist pattern by forming a lower layer film on a substrate using the composition and forming at least one photoresist layer on the lower layer film, Irradiating the region with radiation, and performing development. (A-1) forming a lower layer film using the lower layer film forming material of the present embodiment on a substrate, a step of forming at least one photoresist layer on the lower layer film And (A-2) a step of irradiating a predetermined region of the photoresist layer with radiation after the step (A-2), and performing development.

Further, the circuit pattern forming method of the present embodiment is a method of forming a circuit pattern by forming a lower layer film on a substrate by using the composition, forming an intermediate layer film on the lower layer film by using a resist interlayer film material, A step of forming a photoresist layer of the layer,

Irradiating a predetermined region of the photoresist layer with radiation and developing the resist pattern to form a resist pattern,

Etching the intermediate layer film using the resist pattern as a mask, etching the lower layer film using the obtained intermediate layer film pattern as an etching mask, and etching the substrate using the obtained lower layer film pattern as an etching mask to form a pattern on the substrate do.

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

The forming method of the lower layer film for lithography in the present embodiment is not particularly limited as long as it is formed from the lower layer film forming material of the present embodiment, and a known method can be applied. For example, after the lower layer film material of the present embodiment is applied on a substrate by a known coating method such as spin coating or screen printing, printing or the like, and then the organic solvent is removed by volatilization or the like, And the lower layer film for lithography of the present embodiment can be formed. Examples of the crosslinking method include thermosetting and photo-curing.

At the time of forming the lower layer film, it is preferable to perform baking in order to suppress the occurrence of the mixing phenomenon with the upper layer resist and accelerate the crosslinking reaction. In this case, the bake temperature is not particularly limited, but is preferably in the range of 80 to 450 캜, more preferably 200 to 400 캜. The baking time is not particularly limited, but is preferably in the range of 10 to 300 seconds. On the other hand, the thickness of the lower layer film can be appropriately selected in accordance with the required performance, and is not particularly limited, but is usually about 30 to 20,000 nm, more preferably 50 to 15,000 nm.

In the case of a two-layer process, a silicon-containing resist layer or a single-layer resist made of ordinary hydrocarbon, a silicon-containing intermediate layer on the three-layer process, and a silicon- It is preferable to produce a resist layer. In this case, known photoresist materials for forming the resist layer can be used.

After the lower layer film is formed 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 formed on the lower layer film. In the case of the three-layer process, a silicon-containing intermediate layer on the lower layer film and a single-layer resist layer not containing silicon on the silicon-containing intermediate layer can be produced. In these cases, the photoresist material for forming the resist layer can be appropriately selected from known ones and is not particularly limited.

As a silicon-containing resist material for a two-layer process, a silicon-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as a base polymer from the standpoint of oxygen gas etching resistance, and further, an organic solvent, A positive photoresist material containing a basic compound or the like is preferably used as needed. As the silicon atom-containing polymer, known polymers used in such a resist material can be used.

As the silicon-containing intermediate layer for the three-layer process, an intermediate layer of a polysilsesquioxane base is preferably used. It is possible to effectively suppress reflection by making the intermediate layer have an effect as an antireflection film. For example, in a process for 193 nm exposure, when a material containing a large amount of aromatic groups as a lower layer film and having high substrate etching resistance is used, the k value tends to be high and substrate reflection tends to be high. By suppressing reflection at the intermediate layer, To 0.5% or less. The intermediate layer having such an antireflection effect is not limited to the following, but for the 193 nm exposure, polysilsesquioxane which is crosslinked with acid or heat, into which a light absorbing group having a phenyl group or a silicon-silicon bond is introduced, is preferably used.

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

Furthermore, the lower layer film in the present embodiment can be used as a general antireflection film for single-layer resist or as a foundation material for suppressing pattern collapse. Since the lower layer film is excellent in etching resistance for undercut processing, a function as a hard mask for undercut processing can also be expected.

In the case of forming the resist layer by the photoresist material, a wet process such as spin coating or screen printing is preferably used as in the case of forming the lower layer film. After the resist material is applied by spin coating or the like, prebaking is usually carried out. It is preferable that the prebaking is performed at 80 to 180 DEG C for 10 to 300 seconds. Thereafter, a resist pattern is obtained by performing exposure in accordance with the conventional method, and performing post exposure bake (PEB) and development. On the other hand, the thickness of the resist film is not particularly limited, but is generally from 30 to 500 nm, more preferably from 50 to 400 nm.

The exposure light may be suitably selected in accordance with the photoresist material to be used. Generally, a high energy ray having a wavelength of 300 nm or less, specifically, an excimer laser having a wavelength of 248 nm, 193 nm or 157 nm, a soft X-ray having a wavelength of 3 to 20 nm, an electron beam or an X-ray can be given.

In the resist pattern formed by the above-described method, pattern collapse is suppressed by the lower layer film. Therefore, by using the lower layer film in the present embodiment, a finer pattern can be obtained and the amount of exposure necessary for obtaining the resist pattern can be lowered.

Next, etching is performed using the obtained resist pattern as a mask. As the etching of the lower layer film in the two-layer process, gas etching is preferably used. As gas etching, etching using oxygen gas is favorable. 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 in addition to the oxygen gas. Further, gas etching can be performed using only CO, CO ₂ , NH ₃ , N ₂ , NO ₂ , and H ₂ gas without using oxygen gas. Particularly, the latter gas is preferably used for protecting the side wall for preventing the undercut of the pattern side wall.

On the other hand, also in the etching of the intermediate layer in the three-layer process, gas etching is preferably used. As the gas etching, the same as described in the two-layer process can be applied. Particularly, it is preferable that the processing of the intermediate layer in the three-layer process is carried out using a resist pattern as a mask using a fluorine-based gas. Thereafter, the lower layer film can be processed by performing, for example, oxygen gas etching using the intermediate layer pattern as a mask as described above.

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

As the intermediate layer, an intermediate layer of polysilsesquioxane base is also preferably used. The effect of the antireflection film on the resist interlayer film tends to be able to effectively suppress the reflection. Specific materials of the intermediate layer of the polysilsesquioxane base are not limited to the following examples, but examples thereof include those described in Japanese Patent Application Laid-Open No. 2007-226170 (Patent Document 8) and Japanese Patent Application Laid-Open No. 2007-226204 (Patent Document 9) May be used.

For example, if the substrate is SiO 2 or SiN, the etching can be performed on the following substrate by a conventional method. For example, if the substrate is SiO 2 or SiN, etching is performed using a flon-based gas as a main body, Etching can be performed. When the substrate is etched with a fluorine-based gas, the silicon-containing resist of the two-layer resist process and the silicon-containing intermediate layer of the three-layer process are peeled off simultaneously with the substrate processing. 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 dry etch-off is generally performed with a fron gas after the substrate is processed.

The lower layer film in this embodiment has a feature that the etching resistance of the substrate is excellent. Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, and the like can be given as examples of the substrate to which a known substrate can be suitably selected. Further, the substrate may be a laminate having a workpiece (substrate to be processed) on a substrate (support). Various low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu and Al- And is usually made of a material different from that of the base material (support). On the other hand, the thickness of the substrate or the workpiece to be processed is not particularly limited, but is usually about 50 to 10000 nm, and more preferably 75 to 5000 nm.

[Resist permanent film]

On the other hand, the resist permanent film formed by applying the composition, which can form a permanent resist film by using the above composition, is suitable as a permanent film remaining in the final product after forming a resist pattern if necessary. Specific examples of the permanent film include a thin film transistor protective film, a liquid crystal color filter protective film, and a thin film transistor protective film in the case of a package adhesive layer such as a solder resist, a package material, an underfill material, and a circuit element or an adhesive layer of an integrated circuit element and a circuit board, , A black matrix, a spacer, and the like. Particularly, the permanent film made of the above composition has an excellent advantage of being excellent in heat resistance and moisture resistance, and being less contaminated by sublimation components. In particular, it becomes a material having high sensitivity, high heat resistance, and hygroscopic reliability with less deterioration of image quality due to significant contamination in a display material.

When the composition is used as a resist permanent film application, various additives such as other resins, surfactants, dyes, fillers, crosslinking agents and dissolution accelerators are added, if necessary, in addition to the curing agent, A composition for a film may be used.

The film forming composition for lithography and the composition for a resist permanent film can be adjusted by mixing the above components and mixing them using a stirrer or the like. When the composition for a resist underlayer film or the composition for a resist permanent film contains a filler or a pigment, it can be dispersed or mixed by using a dispersing device such as a dissolver, a homodizer or a 3 roll mill.

Example

Hereinafter, the present embodiment will be described in more detail by way of Synthesis Examples, Synthesis Examples, Examples and Comparative Examples, but the present embodiment is not limited to these Examples at all.

(Carbon concentration and oxygen concentration)

The carbon concentration and oxygen concentration (mass%) were measured by organic element analysis using the following apparatus.

Apparatus: CHN coder MT-6 (manufactured by Yanako Analytical Industry Co., Ltd.)

(Molecular Weight)

The molecular weight of the compound was measured by LC-MS analysis using Acquity UPLC / MALDI-Synapt HDMS manufactured by Water.

Gel permeation chromatography (GPC) analysis was carried out under the following conditions to determine the weight average molecular weight (Mw), the number average molecular weight (Mn) and the degree of dispersion (Mw / Mn) in terms of polystyrene.

Device: Shodex GPC-101 (manufactured by Showa Denko K.K.)

Column: KF-80M x 3

Eluent: THF 1 mL / min

Temperature: 40 ° C

(Solubility)

Dissolve the compound so as to be a 10 mass% solution in propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethylurea The results after one week were evaluated by the following criteria.

Evaluation A: Visually confirming that there is no precipitate in any one of the solvents

Evaluation C: Visually confirming that there is precipitate in all the solvents

[Structure of Compound]

The structure of the compound was confirmed by carrying out < 1 > H-NMR measurement under the following conditions using an Advance 600II spectrometer manufactured by Bruker.

Frequency: 400MHz

Solvent: d6-DMSO

Internal standard: TMS

Measuring temperature: 23 ° C

Synthesis Example 1 Synthesis of XBisN-1

(20 mmol) of 2,6-naphthalene diol (reagent manufactured by Sigma-Aldrich) and 1.82 g (10 mmol) of 4-biphenylcarboxyaldehyde (manufactured by Mitsubishi Gas Chemical Company) were placed in an internal volume of 100 mL equipped with a stirrer, ) Was added to 30 mL of methyl isobutyl ketone, 5 mL of 95% sulfuric acid was added, and the reaction solution was stirred at 100 DEG C for 6 hours to carry out the reaction. Subsequently, the reaction solution was concentrated, and 50 g of pure water was added thereto to precipitate a reaction product. The reaction product was cooled to room temperature, filtered and separated. The resulting solid was filtered, dried and then separated and purified by column chromatography to obtain 3.05 g of the target compound represented by the following formula. It was confirmed by 400 MHz - < ¹ > H-NMR to have the chemical structure of the following formula.

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

(ppm) 9.7 (2H, O-H), 7.2-8.5 (19H, Ph-H), 6.6

On the other hand, the substitution position of the 2,6-naphthalenediol at the 1-position was confirmed by the fact that the signal of the proton at the 3-position and the 4-position was doublet.

(122)

(XBisN-1)

Synthesis Example 2 Synthesis of BisF-1

An internal 200 mL vessel equipped with a stirrer, a cooling tube and a burette was prepared. 30 g (161 mmol) of 4,4-biphenol (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 15 g (82 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co.) and 100 mL of butyl acetate were fed into the vessel, 3.9 g (21 mmol) of p-toluenesulfonic acid (reagent manufactured by Kanto Chemical Co., Ltd.) was added thereto to prepare a reaction solution. The reaction solution was stirred at 90 캜 for 3 hours to carry out the reaction. Next, the reaction solution was concentrated, and 50 g of heptane was added to precipitate the reaction product. The reaction product was cooled to room temperature, filtered, and separated. The solids obtained by filtration were dried and then separated and purified by column chromatography to obtain 5.8 g of the target compound (BisF-1) represented by the following formula.

On the other hand, the following peaks were found by 400 MHz- ¹ H-NMR and it was confirmed that the following chemical structure was obtained.

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

? (ppm) 9.4 (4H, O-H), 6.8-7.8 (22H, Ph-

The molecular weight of the obtained compound was measured by the above-mentioned method and found to be 536.

(123)

(BisF-1)

Synthesis Example 1-1 Synthesis of Al-XBisN-1

9.8 g (21 mmol) of the compound represented by the formula (XBisN-1) and 6.2 g (45 mmol) of potassium carbonate were added to 100 mL of acetone in a container of 100 mL in an internal volume equipped with a stirrer, a cooling tube and a burette , 5.4 g (45 mmol) of allyl bromide and 2.0 g of 10-crown-6 were added, and the resulting reaction solution was stirred under reflux for 7 hours to carry out the reaction. Then, the solid component was removed from the reaction solution by filtration, cooled in an ice bath, and the reaction solution was concentrated to precipitate a solid. The precipitated solid was filtered and dried, and then separated and purified by column chromatography to obtain 4.0 g of the target compound represented by the following formula (Al-XBisN-1).

It was confirmed by 400 MHz - < ¹ > H-NMR to have the chemical structure of the following formula (Al-XBisN-1).

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 7.2 ~ 7.8 ( 19H, Ph-H), 6.7 (1H, CH), 6.1 (2H, -CH = CH 2), 5.4 ~ 5.5 (4H, -CH = CH 2)

The molecular weight of the obtained compound was measured by the above-mentioned method and found to be 546.

(124)

(Al-XBisN-1)

Synthesis Example 2-1 Synthesis of Al-BisF-1

(Al-BisF-1) was obtained in the same manner as in Synthesis Example 1 except that the compound represented by the formula (BisF-1) was used instead of the compound represented by the formula (XBisN-1) To obtain 3.0 g of the desired compound.

It was confirmed by 400 MHz - < ¹ > H-NMR to have the chemical structure of the following formula (Al-BisF-1).

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 6.8 ~ 7.8 ( 22H, Ph-H), 6.2 (1H, CH), 6.1 (4H, -CH = CH 2), 5.4 ~ 5.5 (8H, -CH = CH 2),

The molecular weight of the obtained compound was measured by the above-mentioned method and found to be 872.

(125)

(Al-BisF-1)

<Synthesis Example 1-2> Synthesis of AlOH-XBisN-1

6.1 g (11 mmol) of the compound represented by the formula (Al-XBisN-1) was added to 6.0 mL of an internal volume of 100 mL equipped with a stirrer, a cooling tube and a burette, and the reaction solution was stirred at 130 캜 for 6 hours Thereafter, the temperature was raised to 160 캜 and reaction was carried out for 24 hours. Subsequently, 30 mL of water was added to the reaction solution, the crystals were precipitated and separated by filtration. The resulting solid was filtered, dried and then separated and purified by column chromatography to obtain 0.90 g of the target compound represented by the following formula.

It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula.

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 9.6 (2H, OH), 7.3 ~ 8.5 (17H, Ph-H), 6.6 (1H, CH), 5.9 (2H, -CH = CH 2), 4.9 (4H, -CH = CH 2) _{, 3.8 (4H, -CH 2 -} )

The molecular weight of the obtained compound was measured by the above-mentioned method and found to be 546.

(126)

(AlOH-XBisN-1)

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

Synthesis Example 2-2 Synthesis of AlOH-BisF-1

6.1 g (9 mmol) of the compound represented by the above formula (Al-BisF-1) was added to 6.0 mL of an internal volume of 100 mL equipped with a stirrer, a cooling tube and a burette, and the reaction solution was stirred at 130 캜 for 6 hours Thereafter, the temperature was raised to 160 캜 and reaction was carried out for 24 hours. Subsequently, 30 mL of water was added to the reaction solution, the crystals were precipitated and separated by filtration. The resulting solid was filtered, dried and then separated and purified by column chromatography to obtain 1.05 g of the target compound represented by the following formula.

It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula.

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

(8H, -CH = CH ₂ ), 5.9 (4H, -CH = CH ₂ ), 4.9 (4H, OH), 6.8-7.8 _{, 3.8 (8H, -CH 2 -} )

The molecular weight of the obtained compound was measured by the above-mentioned method and found to be 696.

(127)

(AlOH-BisF-1)

It was confirmed that the thermal decomposition temperature was 390 占 폚 and the glass transition temperature was 200 占 폚 and had high heat resistance.

(Synthesis Examples 3 to 10)

Naphthalene diol and 4-biphenylcarboxyaldehyde, which are raw materials of Synthesis Example 1, were changed to raw materials 1 and 2 of Table 1, and otherwise, the same processes as in Synthesis Example 1 were carried out to obtain respective objects.

Respectively, by 1H-NMR (Table 2).

[Table 1]

[Table 2]

(128)

(XBisN-2)

&Lt; EMI ID =

(XBisN-3)

(130)

(XBisN-4)

[Formula 131]

(XBisN-5)

(132)

(XBisN-6)

(133)

(XBisN-7)

(134)

(XBisN-8)

(135)

(XBisN-9)

(Synthesis Examples 11 to 13)

Naphthalene diol and 4-biphenylcarboxyaldehyde as raw materials of Synthesis Example 1 were changed to raw materials 1 and 2 in Table 3, and 1.5 mL of water, 73 mg (0.35 mmol) of dodecyl mercaptan, 37% (22 mmol) were added to the reaction mixture, and the reaction temperature was changed to 55 캜. The other steps were carried out in the same manner as in Synthesis Example 1 to obtain respective objects.

Respectively, by 1H-NMR.

[Table 3]

[Table 4]

&Lt; EMI ID =

(P-5)

(137)

(P-6)

&Lt; EMI ID =

(P-7)

(Synthesis Examples 3-1 to 13-1)

Synthesis was conducted under the same conditions as in Synthesis Example 1-1 except that the compound represented by the formula (XBisN-1) as the raw material of Synthesis Example 1-1 was changed to the raw material 1 in Table 5, &Lt; / RTI &gt; The structure of each compound was identified by confirming the molecular weight by 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(Synthesis Examples 3-2 to 13-2)

Synthesis was carried out under the same conditions as in Synthesis Example 1-2 except that the compound represented by the formula (Al-XBisN-1) as the raw material of Synthesis Example 1-2 was changed to the raw material 1 in Table 5, , To obtain a target product. The structure of each compound was identified by confirming the molecular weight by 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

[Table 5]

[Chemical Formula 139]

(Al-XBisN-2)

&Lt; EMI ID =

(AlOH-XBisN-2)

(141)

(Al-XBisN-3)

(142)

(AlOH-XBisN-3)

(143)

(Al-XBisN-4)

(144)

(AlOH-XBisN-4)

(145)

(Al-XBisN-5)

(146)

(AlOH-XBisN-5)

(147)

(Al-XBisN-6)

(148)

(AlOH-XBisN-6)

[Chemical Formula 149]

(Al-XBisN-7)

(150)

(AlOH-XBisN-7)

(151)

(Al-XBisN-8)

(152)

(AlOH-XBisN-8)

[Formula 153]

(Al-XBisN-9)

(154)

(AlOH-XBisN-9)

(155)

(Al-P-5)

(156)

(AlOH-P-5)

(157)

(Al-P-6)

(158)

(AlOH-P-6)

(159)

(Al-P-7)

[Formula 160]

(AlOH-P-7)

(Synthesis Example 14) Synthesis of Resin (R1-XBisN-1)

A four liter flask with an internal volume of 1 L, equipped with a Dimros cooling tube, a thermometer and a stirrer, was prepared. 32.0 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound (XBisN-1) obtained in Synthetic Example 1 and 21.0 g of a 40 mass% formalin aqueous solution (280 mmol as formaldehyde, (Manufactured by Kasei Chemical Co., Ltd.) and 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted for 7 hours while refluxing at 100 ° C under atmospheric pressure. Thereafter, 180.0 g of ortho xylene (Wako Pure Chemical Industries, Ltd.) as a diluting solvent was added to the reaction solution, and after standing, the water phase was removed. Again, neutralization and washing were carried out, and ortho-xylene was distilled off under reduced pressure to obtain 34.1 g of a brown solid resin (R1-XBisN-1).

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

(Synthesis Example 15) Synthesis of Resin (R2-XBisN-1)

A four liter flask with an internal volume of 1 L, equipped with a Dimros cooling tube, a thermometer and a stirrer, was prepared. (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 50.9 g (280 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound (XBisN-1) obtained in Synthesis Example 1 (Manufactured by Kanto Chemical Co., Ltd.) and 10 mL of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted for 7 hours while refluxing at 100 ° C under atmospheric pressure. Thereafter, 180.0 g of ortho xylene (Wako Pure Chemical Industries, Ltd.) as a diluting solvent was added to the reaction solution, and after standing, the water phase was removed. The organic phase solvent and unreacted 4-biphenylaldehyde were distilled off under reduced pressure again to obtain 34.7 g of a resin (R2-XBisN-1) as a brown solid.

The obtained resin (R2-XBisN-1) had Mn: 1610, Mw: 2567, and Mw / Mn: 1.59.

<Synthesis Example 14-1> Synthesis of Al-R1-XBisN-1

30 g of the resin (R1-XBisN-1) represented by the above-described formula and 29.6 g (214 mmol) of potassium carbonate were added to 100 ml of dimethylformamide in a container having an internal volume of 500 ml equipped with a stirrer, a cooling tube and a burette, 2-Chloroethyl 13.12 g (108 mmol) was added, and the reaction solution was stirred at 90 占 폚 for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the above crystals, 80 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were charged into a container having an internal volume of 100 ml equipped with a stirrer, a cooling tube and a burette, and the reaction solution was stirred under reflux for 4 hours to carry out the reaction. Thereafter, the solution was cooled in an ice bath and the reaction solution was concentrated. The precipitated solid was filtered and dried to obtain 26.5 g of a brown solid resin (Al-R1-XBisN-1).

The obtained resin (Al-R1-XBisN-1) had Mn of 2076, Mw of 3540, and Mw / Mn.

<Synthesis Example 14-2> Synthesis of AlOH-R1-XBisN-1

20.0 g of the resin represented by the above formula (R1-XBisN-1) and 12.8 g of vinylbenzyl chloride (trade name: CMS-P, manufactured by Seiyam Chemical Co., Ltd.) were added to a container having an internal volume of 500 ml equipped with a stirrer, Was added to 200 ml of dimethylformamide and 16.0 g of 28 wt% sodium methoxide (methanol solution) was added thereto from the dropping funnel over 20 minutes while being heated to 50 캜 and stirred. The reaction solution was stirred at 50 캜 for 1 hour And the reaction was carried out. Subsequently, 3.2 g of 28 wt% sodium methoxide (methanol solution) was added, and the reaction solution was heated at 60 캜 and stirred for 5 hours. Further, 2.4 g of 85 wt% phosphoric acid was added and stirred for 10 minutes. , The reaction solution was added dropwise to pure water, and the precipitated solid was filtered, and then dried. The reaction solution was cooled to 50 ° C and the reaction solution was added dropwise to the pure water. The precipitated solid was filtered and dried. -XBisN-1). &Lt; / RTI &gt;

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

Synthesis Example 15-1 Synthesis of Al-R2-XBisN-1

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

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

Synthesis Example 15-2 Synthesis of AlOH-R2-XBisN-1

40.5 g of the compound represented by the formula (Al-R2-XBisN-1) obtained in Synthesis Example 15-1 was used in place of the formula (Al-R1-XBisN-1) obtained in Synthesis Example 14-1 Was reacted in the same manner as in Synthesis Example 14-2 to give 36.8 g of a pale gray solid (AlOH-R2-XBisN-1) resin.

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

<Synthesis Comparative Example 1>

A four-necked flask with an inner volume of 10 L was provided with a bottom-detachable flask equipped with a Dimros cooling tube, a thermometer and a stirrer. To this four-necked flask, 1.09 kg (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of 1,5-dimethylnaphthalene, 2.1 kg (40 mol% formaldehyde solution: 28 mol, manufactured by Mitsubishi Gas Chemical Co., ) And 0.97 mL of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), and the reaction was carried out for 7 hours while refluxing at 100 DEG C under normal pressure. Thereafter, 1.8 kg of ethylbenzene (a reagent grade manufactured by Wako Pure Chemical Industries, Ltd.) as a diluting solvent was added to the reaction solution, and after standing, the water phase of the bed was removed. Then, neutralization and washing were carried out, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a dimethylnaphthalene formaldehyde resin having a pale brown solid.

The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562.

Subsequently, an inner volume 0.5 L four-necked flask equipped with a Dimros cooling tube, a thermometer and a stirring blade was prepared. 100 g (0.51 mol) of the dimethyl naphthalene formaldehyde resin obtained as described above and 0.05 g of paratoluene sulfonic acid were introduced into the four-necked flask under a nitrogen stream. The mixture was heated to 190 DEG C and heated for 2 hours and stirred. Thereafter, again 52.0 g (0.36 mol) of 1-naphthol was added, and the temperature was raised to 220 ° C and reacted for 2 hours. After solvent dilution, neutralization and washing were carried out, and the solvent was removed under reduced pressure to obtain 126.1 g of a modified resin (CR-1) as a dark brown solid.

The obtained resin (CR-1) had Mn of 885, Mw of 2220 and Mw / Mn of 4.17. The carbon concentration was 89.1 mass% and the oxygen concentration was 4.5 mass%.

[Examples 1-1 to 15-2, Comparative Example 1]

The solubility test was carried out using the compound or resin described in Synthesis Examples 1-1 to 15-2 and CR-1 described in Synthesis Comparative Example 1. The results are shown in Table 6.

Further, the lower layer film forming materials for lithography having compositions shown in Table 6 were prepared. Subsequently, these lower layer film forming materials for lithography were spin-coated on the silicon substrate, and then baked at 240 캜 for 60 seconds and then at 400 캜 for 120 seconds to prepare lower layer films each having a film thickness of 200 nm. The following acid generators, crosslinking agents and organic solvents were used.

Acid generator: ditertiary butyl diphenyl iodonium nonafluoromethane sulphonate (DTDPI) manufactured by Midori Kagaku Co.,

Crosslinking agent: NIKARAK MX270 (NIKARAK) manufactured by SANWA CHEMICAL CO.

Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA)

· NOVOLAC: PSM4357 manufactured by Gun-ei Chemical Co., Ltd.

Further, materials for forming a lower layer film for lithography having the compositions shown in Table 7 were prepared. Next, these coated lithographic rotate the lower layer film formation material for the silicon substrate, and thereafter, after removal of the solvent in the coating film by baking at 110 ℃ 60 seconds, with a high-pressure mercury lamp, light exposure integrator 600mj / cm ^2, irradiation And the time was 20 seconds to prepare a lower layer film having a film thickness of 200 nm. For the photoacid generator, crosslinking agent and organic solvent, the following were used.

Radical polymerization initiator: IRGACURE 184 manufactured by BASF

· Cross-linking agent: Mitsubishi gasification agent diallyl bisphenol A cyanate (DABPA-CN)

Diallyl bisphenol A (BPA-CA) manufactured by Konishi Chemical Industry Co.,

Benzooxane photo (BF-BXZ) manufactured by Konishi Chemical Industry Co.,

Biphenyl aralkyl type epoxy resin (NC-3000-L)

Organic solvent: propylene glycol monomethyl ether acetate acetate (PGMEA)

The structure of the crosslinking agent is represented by the following formula.

[Formula 161]

(DABPA-CN)

(162)

(BPA-CA)

[163]

(BF-BXZ)

&Lt; EMI ID =

(Wherein n is an integer of 1 to 4)

(NC-3000-L)

[Etching Resistance]

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

[Etching test]

Etching apparatus: RIE-10NR manufactured by SAMCO INTERNATIONAL

Output: 50W

Pressure: 20 Pa

Time: 2min

Etching gas

Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)

The evaluation of the etching resistance was carried out in the following order.

First, a novolak underlayer film was prepared under the same conditions as in Example 1, except that novolac (PSM4357, manufactured by Gunze Chemical Co., Ltd.) was used instead of the compound (AlOH-XBisN-1). The lower layer film of the novolak was subjected to the above etching test, and the etching rate at that time was measured.

Next, the lower layer films of Examples 1-1 and 2 and Comparative Example 1 were subjected to the same etching test, and the etching rate at that time was measured. Then, with respect to the etching rate of the novolac underlayer film, the etching resistance was evaluated based on the following evaluation criteria.

[Evaluation standard]

A: Less than -10% etch rate compared to novolak underlayer film

B: an etching rate of -10% to + 5% as compared with the lower layer film of novolak;

C: The etching rate exceeds + 5% as compared with the novolac underlayer film.

[Table 6]

[Table 7]

&Lt; Examples 38 to 39 >

Next, each solution of the lower layer film forming material for lithography, which was obtained in Examples 1-1 and 2-1 and containing AlOH-XBisN-1 or AlOH-BisF-1, was applied onto a SiO ₂ substrate with a film thickness of 300 nm And baked at 240 캜 for 60 seconds and again at 400 캜 for 120 seconds to form a lower film having a film thickness of 70 nm. On this lower layer film, a resist solution for ArF was applied and baked at 130 캜 for 60 seconds to form a photoresist layer having a thickness of 140 nm. On the other hand, as the ArF resist solution, 5 parts by mass of the compound of the following formula (11), 1 part by mass of triphenylsulfonium nonafluoromethane sulfonate, 2 parts by mass of tributylamine, and 92 parts by mass of PGMEA Were used.

The compound of the formula (11) was prepared by reacting 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy- gamma -butyrolactone, 3.00 g of 3-hydroxy- 2.08 g of the compound and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to prepare a reaction solution. The reaction solution was polymerized for 22 hours while maintaining the reaction temperature at 63 캜 in a nitrogen atmosphere, and then the reaction solution was added dropwise to 400 mL of n-hexane. The resultant resin thus obtained was coagulated and purified, and the resulting white powder was filtered and dried overnight at 40 캜 under reduced pressure.

(165)

(11)

In the formula (11), "40", "40" and "20" represent the ratio of each constitutional unit and do not represent a block copolymer.

Subsequently, the photoresist layer was exposed using an electron beam imaging apparatus (ELO-7500, 50 keV, manufactured by Elionix), baked (PEB) at 115 캜 for 90 seconds, and 2.38 mass% tetramethylammonium hydroxide (TMAH) And then developed with an aqueous solution for 60 seconds to obtain a positive resist pattern.

The shapes and defects of the obtained resist patterns of 55 nm L / S (1: 1) and 80 nm L / S (1: 1) were observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd.

Regarding the shape of the resist pattern after development, evaluation was made for "no pattern collapse", "good" for good rectangularity and "poor" for other. As a result of the above observation, the minimum line width with no pattern collapse and good rectangularity was regarded as an index of evaluation as &quot; resolution. &Quot; The minimum amount of electron beam energy capable of drawing a good pattern shape was defined as &quot; sensitivity &quot;

The evaluation results are shown in Table 8.

&Lt; Comparative Example 2 &

A photoresist layer was formed directly on the SiO ₂ substrate in the same manner as in Example 38 except that formation of the lower layer film was not performed, and a positive resist pattern was obtained. The results are shown in Table 8.

[Comparative Example 2]

[Table 8]

As is apparent from Table 8, it was confirmed that in the examples using the lower layer film forming material containing the compound of this embodiment, the resist pattern shape after development was good and no defects were seen. It was confirmed that both the resolution and the sensitivity were significantly superior to those of Comparative Example 2 in which formation of the lower layer film was omitted.

From the difference in shape of the resist pattern after development, it was found that the lower layer film forming material for lithography used in Examples 38 to 39 had good adhesion to a resist material.

As is clear from Table 1, in Examples 1-1 and 2-1 using AlOH-XBisN-1 or AlOH-BisF-1, it is preferable that all of the heat resistance, the solubility and the etching resistance are better than those of Comparative Example 1 . On the other hand, in Comparative Example 1 using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resin), the etching resistance was poor.

It was also confirmed in Examples 38 to 39 that the shape of the resist pattern after development was satisfactory and no defects were seen. Furthermore, it was confirmed that both the resolution and the sensitivity were significantly superior to those of Comparative Example 2 in which formation of the underlayer film was omitted.

It was also confirmed from the difference in shape of the resist pattern after development that the lower layer film forming material for lithography used in Examples 38 to 39 had good adhesion to the resist material.

&Lt; Examples 40 to 41 &

A solution of the lower layer film forming material for lithography of Examples 1-1 and 2-1 using AlOH-XBisN-1 or AlOH-BisF-1 was coated on a SiO ₂ substrate having a film thickness of 300 nm, And further baked at 400 DEG C for 120 seconds to form a lower film having a film thickness of 80 nm. A silicon-containing intermediate layer material was coated on the lower layer film and baked at 200 캜 for 60 seconds to form an intermediate layer film having a film thickness of 35 nm. The resist solution for ArF was coated on the intermediate layer film and baked at 130 캜 for 60 seconds to form a photoresist layer having a film thickness of 150 nm. On the other hand, as the silicon-containing intermediate layer material, the silicon atom-containing polymer obtained as described below was used.

16.6 g of 3-carboxylpropyltrimethoxysilane, 7.9 g of phenyltrimethoxysilane and 14.4 g of 3-hydroxypropyltrimethoxysilane were dissolved in 200 g of tetrahydrofuran (THF) and 100 g of pure water, and the solution temperature was 35 Deg.] C, 5 g of oxalic acid was added dropwise, and then the temperature was raised to 80 DEG C to carry out a condensation reaction of silanol. Next, 200 g of diethyl ether was added and the water layer was separated. The organic liquid layer was washed twice with ultra pure water, and 200 g of propylene glycol monomethyl ether acetate (PGMEA) was added. While the liquid temperature was being raised to 60 占 폚, Ethyl ether water was removed to obtain a silicon atom-containing polymer.

Subsequently, the photoresist layer was exposed to a mask using an electron beam imaging apparatus (ELI-7500, 50 keV, manufactured by Elionics), baked (PEB) at 115 DEG C for 90 seconds and then immersed in 2.38 mass% tetramethylammonium hydroxide ) Aqueous solution for 60 seconds to obtain a positive resist pattern of 55 nm L / S (1: 1).

Thereafter, dry etching of the silicon-containing intermediate layer film (SOG) was performed using RIE-10NR manufactured by Sanko International Co., using the obtained resist pattern as a mask, and then dry etching of the lower layer film using the obtained silicon- Etching processing, and dry etching processing of the SiO ₂ film using the obtained lower layer film pattern as masks.

The respective etching conditions are as follows.

Etching conditions for the resist interlayer film of the resist pattern

Output: 50W

Pressure: 20 Pa

Time: 1min

Etching gas

Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 8: 2 (sccm)

Etching conditions for resist lower layer film of resist interlayer film pattern

Output: 50W

Pressure: 20 Pa

Time: 2min

Etching gas

Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)

The resist underlayer film pattern SiO ₂ Etching conditions for the film

Output: 50W

Pressure: 20 Pa

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]

As a result of observing the pattern end face thus obtained (the shape of the SiO ₂ film after etching) using an electron microscope (S-4800) manufactured by Hitachi, Ltd., the example using the lower layer film of the present embodiment, It was confirmed that the shape of the SiO ₂ film after etching in the processing was rectangular, and no defects were seen, and that it was good.

[Examples 42 to 45]

Using the respective compounds synthesized in the above Synthesis Examples, optical component forming compositions were prepared in the formulations shown in Table 9 below. On the other hand, the following components were used for the acid generator, the crosslinking agent, the acid diffusion inhibitor and the solvent in the respective components of the optical component forming composition shown in Table 9.

Acid generator: ditertiary butyl diphenyl iodonium nonafluoromethane sulphonate (DTDPI) manufactured by Midori Kagaku Co.,

Crosslinking agent: NIKARAK MX270 (NIKARAK) manufactured by SANWA CHEMICAL CO.

Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)

The optical component-forming composition in a uniform state was spin-coated on a clean silicon wafer and then prebaked (PB) in an oven at 110 캜 to form an optical component-forming film having a thickness of 1 탆. The prepared optical component-forming composition was evaluated as "A" when the film formation was good and "C" when the film was defective.

A uniform optical component-forming composition was spin-coated on a clean silicon wafer, and then the film was baked in an oven at 110 캜 to form a film having a thickness of 1 탆. For the film, the refractive index (? = 589.3 nm) at 25 占 폚 was measured with a spectroscopic ellipsometer VASE of the? The prepared film was evaluated as "A" when the refractive index was 1.65 or more, "B" when the refractive index was 1.6 or more but less than 1.65, and "C" when the refractive index was less than 1.6. When the transparency (? Nm) was 90% or more, it was evaluated as "A" and when it was less than 90%, it was evaluated as "C".

[Table 9]

[Examples 46 to 49]

Using the respective compounds synthesized in Synthesis Examples and Synthesis Examples, a resist composition was prepared in the formulations shown in Table 10 below. On the other hand, of the components of the resist composition in Table 10, the following were used for the radical generator, the radical diffusion inhibitor, and the solvent.

Radical polymerization initiator: IRGACURE 184 manufactured by BASF

Radical Diffusion Control Agent: IRGACURE1010 manufactured by BASF

Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)

[Assessment Methods]

(1) Storage stability and thin film formation of resist composition

The storage stability of the resist composition was evaluated by observing the presence or absence of precipitation with naked eyes after the resist composition was prepared and allowed to stand at 23 캜 and 50% RH for 3 days. In the resist composition after standing for 3 days, A was evaluated as a homogeneous solution when there was no precipitation, and C when precipitation was observed. Further, the resist composition in a uniform state was spin-coated on a clean silicon wafer, and then baked (PB) in an oven at 110 캜 before exposure to form a resist film having a thickness of 40 nm. The prepared resist composition was evaluated as A when the film formation was good and C when the film formed was defective.

(2) Evaluation of pattern of resist pattern

A uniform resist composition was spin-coated on a clean silicon wafer, and then baked (PB) in an oven at 110 캜 before exposure to form a resist film having a thickness of 60 nm. The resulting resist film was irradiated with electron beams at a 1: 1 line-and-space setting of 50 nm, 40 nm, and 30 nm intervals using an electron beam drawing apparatus (ELS-7500, Elionics Inc.). After the irradiation, the resist film was heated at a predetermined temperature for 90 seconds and immersed in PGME for 60 seconds to carry out development. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern. The resist pattern thus formed was observed by a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Co., Ltd.) and the reactivity of the resist composition by electron beam irradiation was evaluated.

The sensitivity was expressed by the minimum amount of energy per unit area required to obtain the pattern and evaluated according to the following.

A: When the pattern is obtained at less than 50 μC / cm 2

C: When a pattern is obtained at 50 μC / cm 2 or more

In pattern formation, the obtained pattern shape was observed with an SEM (Scanning Electron Microscope) and evaluated according to the following.

A: When a rectangular pattern is obtained

B: When a substantially rectangular pattern is obtained

C: When a non-rectangular pattern is obtained

[Table 10]

As described above, the present invention is not limited to the above-described embodiments and examples, and it is possible to modify it appropriately within a range not departing from the gist of the present invention.

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

In addition, compounds, resins, and film forming compositions for lithography that are useful for forming a photoresist undercoat film to which a wet process can be applied and which are excellent in heat resistance and etching resistance can be realized. Since the film forming composition for lithography uses a compound or resin having a specific structure and high heat resistance and high solvent solubility, deterioration of the film at the time of high-temperature baking is suppressed and etching resistance against oxygen plasma etching and the like is also excellent A resist and a lower layer film can be formed. Furthermore, when a lower layer film is formed, adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed.

Further, it is useful as a composition for forming various optical parts in that the refractive index is high and the coloration is suppressed by the treatment at a low temperature to a high temperature.

Therefore, the present invention is applicable to, for example, electric insulating materials, resist resins, sealing resins for semiconductors, adhesives for printed wiring boards, electric laminated boards mounted on electric devices, Resin for resin for fiber reinforced plastic, resin for encapsulating liquid crystal display panel, coating material, coating agent, adhesive, coating material for semiconductor, resin for resist for semiconductor, lower layer of matrix resin, build-up laminate material, (Prism lens, lenticular lens, micro lens, Fresnel lens, viewing angle control lens, contrast enhancement lens, etc.), a retardation film, a film for electromagnetic wave shielding, Prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, optical parts such as photosensitive optical waveguides, etc. Method, it is possible to use widely available as well.

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2016-178433) filed on September 13, 2016, the contents of which are incorporated herein by reference.

Industrial availability

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

Claims (28)

(0). &Lt; / RTI &gt;
[Chemical Formula 1]

(0)
(In the formula (0), R ^Y is a hydrogen atom,
R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms,
R ^T each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond or an ester bond Wherein at least one of R ^T is a hydroxyl group and at least one of R ^T is an alkenyl group having 2 to 30 carbon atoms,
X represents an oxygen atom, a sulfur atom, a single bond or a non-condensed,
m is independently an integer of 0 to 9, provided that at least one of m is an integer of 2 to 9, or at least two of m is an integer of 1 to 9,
N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas within N [] may be the same or different,
r is independently an integer of 0 to 2.) The method according to claim 1,
Wherein the compound represented by the formula (0) is a compound represented by the following formula (1).
(2)

(One)
(In the formula (1), R ⁰ is the same as R ^Y ,
R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms,
R ² to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond Or at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms,
m ² and m ³ are each independently an integer of 0 to 8,
m ⁴ and m ⁵ are each independently an integer of 0 to 9 with the proviso that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time, m ² , m ³ , m ⁴ and m ⁵ At least one of them is an integer of 2 to 8 or 2 to 9, or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9,
When n is an integer of 2 or more, the structural formulas within n [] may be the same or different,
and p ² to p ⁵ each independently denote the same as r. The method according to claim 1,
Wherein the compound represented by the formula (0) is a compound represented by the following formula (2).
(3)

(2)
(In the formula (2), R ^0A is the same as the above R ^Y ,
R ^1A is an n ^A -valent group or a single bond having 1 to 30 carbon atoms,
R ^2A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond or an ester bond Wherein at least one of R ^2A is at least one hydroxyl group and at least one of R ^2A is an alkenyl group having 2 to 30 carbon atoms,
n ^A is a consensus with the above N, wherein, when n ^A is an integer of 2 or more, the structural formulas in n ^A [] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom, a single bond or a non-condensed,
m ^2A is independently an integer of 0 to 7, provided that at least one of m ^2A is an integer of 2 to 7 or at least two of m ^2A is an integer of 1 to 7,
q ^A are each independently 0 or 1.) 3. The method of claim 2,
Wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).
[Chemical Formula 4]

(1-1)
(In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are the same as above,
R ⁶ to R ⁷ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, An atom, a nitro group, an amino group, a carboxylic acid group or a thiol group, wherein at least one of R ⁶ to R ⁷ is an alkenyl group having 2 to 30 carbon atoms,
R ¹⁰ to R ¹¹ are each independently a hydrogen atom,
m ⁶ and m ⁷ are each independently an integer of 0 to 7 with the proviso that m ⁴ , m ⁵ , m ⁶ and m ⁷ do not become 0 at the same time. 5. The method of claim 4,
Wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).
[Chemical Formula 5]

(1-2)
(Wherein R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are as defined above,
R ⁸ to R ⁹ are as defined above for R ⁶ to R ⁷ ,
R ¹² to R ¹³ are as defined above for R ¹⁰ to R ¹¹ ,
m ⁸ and m ⁹ are each independently an integer of 0 to 8, provided that m ⁶ , m ⁷ , m ⁸ and m ⁹ do not become 0 at the same time. The method of claim 3,
Wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).
[Chemical Formula 6]

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

(3)
(In the formula (3), L represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, An alkoxylene group or a single bond having 1 to 30 carbon atoms, and the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R ⁰ is synonymous with R ^Y above,
R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms,
R ² to R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond Or an ester bond, wherein at least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms,
m ² and m ³ are each independently an integer of 0 to 8,
m ⁴ and m ⁵ are each independently an integer of 0 to 9 with the proviso that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time, m ² , m ³ , m ⁴ and m ⁵ Is an integer of 2 to 8 or 2 to 9, or at least two of m ² , m ³ , m ⁴ and m ⁵ is an integer of 1 to 8 or 1 to 9.) 8. The method of claim 7,
Having a structure represented by the following formula (4).
[Chemical Formula 8]

(4)
(In the formula (4), L represents a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond,
R ^0A is synonymous with R ^Y above,
R ^1A is an n ^A -valent group or a single bond having 1 to 30 carbon atoms,
R ^2A each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, A halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have an ether bond, a ketone bond or an ester bond , Wherein at least one of R ^2A is a hydroxyl group, and at least one of R ^2A is an alkenyl group having 2 to 30 carbon atoms,
n ^A is a consensus with the above N, wherein, when n ^A is an integer of 2 or more, the structural formulas in n ^A [] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom, a single bond or a non-condensed,
m ^2A is independently an integer of 0 to 7, provided that at least one of m ^2A is an integer of 2 to 7 or at least two of m ^2A is an integer of 1 to 7,
q ^A are each independently 0 or 1.) A composition comprising at least one compound selected from the group consisting of the compound according to any one of claims 1 to 6 and the resin according to any one of claims 7 to 9. 11. The method of claim 10,
Wherein the composition further comprises a solvent. The method according to claim 10 or 11,
&Lt; / RTI &gt; further comprising an acid generator. 13. The method according to any one of claims 10 to 12,
Wherein the composition further comprises a crosslinking agent. 14. The method of claim 13,
Wherein the crosslinking agent is at least one selected from the group consisting of phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds and azide compounds Lt; / RTI &gt; The method according to claim 13 or 14,
Wherein the crosslinking agent has at least one allyl group. 16. The method according to any one of claims 13 to 15,
Wherein the content of the crosslinking agent is 0.1 to 50 mass% of the total mass of the solid component. 17. The method according to any one of claims 13 to 16,
Wherein the composition further comprises a crosslinking accelerator. 18. The method of claim 17,
Wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids. The method according to claim 17 or 18,
Wherein the content of the crosslinking accelerator is 0.1 to 5 mass% of the total mass of the solid component. 20. The method according to any one of claims 10 to 19,
Further comprising a radical polymerization initiator. 21. The method according to any one of claims 10 to 20,
Wherein the radical polymerization initiator is 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. 22. The method according to any one of claims 10 to 21,
Wherein the content of the radical polymerization initiator is 0.05 to 25 mass% of the total mass of the solid component. 23. The method according to any one of claims 10 to 22,
A composition for use in forming a film for lithography. 23. The method according to any one of claims 10 to 22,
A composition for use in resist permanent film formation. 23. The method according to any one of claims 10 to 22,
A composition for use in forming an optical component. A method for forming a resist pattern, comprising: forming a photoresist layer on a substrate using the composition according to claim 23; and irradiating a predetermined region of the photoresist layer with radiation to perform development. Forming a lower layer film on the substrate using the composition according to claim 23, forming at least one photoresist layer on the lower layer film, irradiating a predetermined region of the photoresist layer with radiation, Thereby forming a resist pattern. Forming a lower layer film on the substrate using the composition according to claim 23, forming an intermediate layer film on the lower layer film using a resist interlayer film material, and forming at least one photoresist layer on the intermediate layer film And then the resist pattern is used as a mask to etch the intermediate layer film, and the obtained intermediate layer film pattern is etched using an etching mask And etching the substrate using the obtained lower layer film pattern as an etching mask to form a pattern on the substrate.