TW201827418A - Compound, resin, composition, method for forming resist pattern, and method for forming circuit pattern - Google Patents

Abstract

The invention provides a compound represented by the following formula (0), (in formula (0), R<SP>Y</SP> represents a hydrogen atom; R<SP>Z</SP> represents a N-valent group having 1 to 60 carbon atoms or a single bond; R<SP>T</SP> each independently represents an alkyl group having 1 to 30 carbon atoms which may have substitution, an aryl group having 6 to 30 carbon atom which may have substitution, an alkenyl group having 2 to 30 carbon atoms which may have substitution, an alkoxy group having 1 to 30 carbon atoms which may have substitution, a halogen atom, a nitro group, an amino group, a carboxyl group, a thiol group or a hydroxyl group, wherein said alkyl, aryl, alkenyl and alkoxy groups may contain an ether bond, a keto bond or an ester bond, and wherein at least one R<SP>T</SP> represents a hydroxyl group and at least one R<SP>T</SP> represents an alkenyl group having 2 to 30 carbon; X represents an oxygen atom, a sulfur atom, a single bond or is uncrosslinked; m each independently is an integer of 0 to 9, wherein at least one m is an integer of 1 to 9 or at least two m's are an integer of 1 to 9; N is an integer of 1 to 4, and when N is an integer of 2 or greater, the structural formulae included in N [ ]'s may be the same or different; and r each independently represents an integer of 0 to 2.).

Description

 Compound, resin, composition, resist pattern forming method and circuit 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 manufacture of a semiconductor device, the microfabrication by photolithography is carried out. However, in recent years, with the high integration and high speed of LSI, further miniaturization by pattern specifications is expected. . Further, the light source for lithography used in the formation of the resist pattern is short-wavelength from the KrF excimer laser (248 nm) to the ArF excimer laser (193 nm), and the introduction of extreme ultraviolet light (EUV, 13.5 nm) is also Forecasting.

However, in the photolithography using the conventional polymer-based resist material, the molecular weight is as large as 10,000 to 100,000, and the molecular weight distribution is also wide, so that the control of the pattern size on the surface of the pattern is generated. Difficult to change, miniaturization has limits. Heretofore, various types of low molecular weight resist materials have been proposed in order to impart a higher resolution resist pattern. Since the molecular size of the low molecular weight resist material is small, it is expected to provide a resist pattern having high resolution and low roughness.

As such a low molecular resistance resist material, various kinds are known. For example, an alkali-developing negative-type radiation-sensitive linear composition using a low-molecular-weight polynuclear polyphenol compound as a main component (for example, refer to Patent Document 1 and Patent Document 2) has been proposed as a low-molecular-weight resist material having high heat resistance. As a candidate, an alkali-developing negative-type radiation-sensitive linear composition using a low molecular weight cyclic polyphenol compound as a main component has been proposed (for example, refer to Patent Document 3 and Non-Patent Document 1). Further, as a base compound of the resist material, the polyphenol compound has a low molecular weight and can impart high heat resistance, and is known to be used as an improvement in resist pattern resolution or roughness (for example, refer to Non-Patent Document 2).

The present inventors have hitherto been known as a material having excellent etching resistance and being soluble in a solvent and suitable for a wet process, and a resist composition containing a compound having a specific structure and an organic solvent (for example, a reference patent) Document 4).

Further, if the resist pattern miniaturization is continued, there is a problem of resolution or a problem of dumping the resist pattern after development, and thus the film of the resist is expected to be thinned. However, when only the resist thin film formation is performed, it becomes difficult to obtain a sufficient resist pattern thickness on the substrate processing. Therefore, a resist underlayer film is formed not only for the resist pattern but also between the resist and the processed semiconductor substrate, and the underlayer film is also provided with a function as a mask for processing the substrate. Become a must.

Various types of underlayer films for such processes are known. For example, as a resist underlayer film for lithography which is different from the resist underlayer film which has a fast etching speed in the past and has a selection ratio close to the dry etching speed of the resist, it has been proposed to contain at least a predetermined energy by input. The underlayer film forming material for a multilayer resist process for forming a resin component having a substituent of a sulfonic acid residue after detachment with a solvent (for example, refer to Patent Document 5). Further, as a resist underlayer film for lithography which has a selection ratio of a dry etching rate which is smaller than that of a resist, a resist underlayer film material containing a polymer having a specific repeating unit has been proposed (for example, a reference patent) Document 6). Further, as a resist underlayer film for lithography which has a smaller selection ratio of dry etching speed than a semiconductor substrate, it has been proposed to repeat a repeating unit containing a copolymerized terpene and a substituted or unsubstituted hydroxyl group. A resist underlayer film material of a polymer formed by a unit (for example, refer to Patent Document 7).

On the other hand, as the material having high etching resistance, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas or the like as a raw material is known. However, from the viewpoint of the process, a resist underlayer film material which can form a resist underlayer film by a wet process such as a spin coating method or screen printing is expected.

Further, the inventors of the present invention have proposed a lower layer for lithography containing a compound having a specific structure and an organic solvent, which is excellent in heat resistance and soluble in a solvent, and which is suitable for a wet process. A film forming composition (for example, refer to Patent Document 8).

Further, regarding a method of forming an intermediate layer used for formation of a resist underlayer film in a three-layer process, for example, a method of forming a tantalum nitride film (for example, refer to Patent Document 9) or a CVD of a tantalum nitride film is known. Method (for example, refer to Patent Document 10). Further, as the intermediate layer material for the three-layer process, a material containing a sesquiterpoxyalkyl group-based oxime compound is known (for example, refer to Patent Documents 11 and 12).

The optical component forming composition has been proposed, and examples thereof include an acrylic resin (for example, refer to Patent Documents 13 to 14) or a polyphenol having a specific structure derived from an allyl group (for example, refer to Patent Document 15).

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] JP-A-2005-326838

[Patent Document 2] JP-A-2008-145539

[Patent Document 3] JP-A-2009-173623

[Patent Document 4] International Publication No. 2013/024778

[Patent Document 5] JP-A-2004-177668

[Patent Document 6] JP-A-2004-271838

[Patent Document 7] JP-A-2005-250434

[Patent Document 8] International Publication No. 2013/024779

[Patent Document 9] JP-A-2002-334869

[Patent Document 10] International Publication No. 2004/066377

[Patent Document 11] JP-A-2007-226170

[Patent Document 12] JP-A-2007-226204

[Patent Document 13] JP-A-2010-138393

[Patent Document 14] JP-A-2015-174877

[Patent Document 15] International Publication No. 2014/123005

 [Non-patent literature]  

[Non-Patent Document 1] T. Nakayama, M. Nomura, K. Haga, M. Ueda: Bull. Chem. Soc. Jpn., 71, 2979 (1998)

[Non-Patent Document 2] 22 "New Development of Photoresist Materials Development" by Megaki Shinji, published by CMC Corporation, September 2009, p.211-259

As described above, in the past, many lithographic film forming compositions for resist use and lithographic film forming compositions for use in underlayer films have been proposed, but they are not only applicable to spin coating or screen printing. We are looking forward to the development of new materials because of the high solvent solubility of the wet process and the fact that it does not have heat resistance and etching resistance at high temperatures.

Further, although many compositions for optical members have been proposed in the past, heat resistance, transparency, and refractive index have not been obtained in a high degree, and development of novel materials is expected.

The present invention has been made in view of the above-mentioned problems of the prior art, and it is an object of the present invention to provide a compound and a resin which are useful in a wet process and which are formed on an underlayer film for photoresist and photoresist which are excellent in heat resistance, solubility, and etching resistance. And composition.

The inventors of the present invention have solved the above-mentioned problems of the prior art and have carried out repeated detailed review and found that the above-described problems of the prior art can be solved by a compound or a resin having a specific structure, and the present invention has been completed.

That is, the present invention is as follows.

[1]

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 of R ^{T is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have The aryl group having 6 to 30 carbon atoms of the substituent, the alkenyl group having 2 to 30 carbon atoms which may have a substituent, the alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl group, the aforementioned alkenyl group and the alkoxy group may contain an ether bond, a keto bond or an ester bond, wherein at least one of R ^T is a hydroxyl group and R ^T At least one of them is an alkenyl group having 2 to 30 carbon atoms, and X represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, and each m is independently an integer of 0 to 9, wherein at least one of m is 2 to 9 At least two integers or m are integers from 1 to 9, and N is an integer from 1 to 4. When N is an integer of 2 or more, the structural formulas in N [ ] may be the same or different, r Independently an integer from 0 to 2)

[2]

The compound represented by the above formula (0) is a compound described in [1] of the compound represented by the following formula (1).

(In the formula (1), R ⁰ has the same meaning as the above R ^Y , R ¹ is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of R ² to R ^{5 is} independently a carbon number of 1 to 30 which may have a substituent. An alkyl group, 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 alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, and a nitrate a group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the aforementioned alkoxy group may have an ether bond, a keto bond or an ester bond, wherein R ² to R ⁵ At least one of the hydroxyl groups, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms, and m ² and m ^{3 are} each independently an integer of 0 to 8, and m ⁴ and m ^{5 are} each independently 0 to 0. An integer of 9 but m ² , m ³ , m ⁴ and m ^{5 are} not 0 at the same time, and at least one of m ² , m ³ , m ⁴ and m ⁵ is an integer of 2-8 or 2-9 or m ² At least two of m ³ , m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9, and n is synonymous with the above N. When n is an integer of 2 or more, the structural formulas in n [ ] may be The same or different, p ² ~ p ^{5 are} each independently synonymous with the aforementioned r.)

[3]

The compound represented by the above formula (0) is a compound described in [1] of the compound represented by the following formula (2).

(In the formula (2), R ^{0A is} synonymous with the above R ^Y , R ^1A is an n ^A valent group or a single bond having 1 to 30 carbon atoms, and each of R ^{2A is} independently 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 alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, An amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the aforementioned alkoxy group may have an ether bond, a keto bond or an ester bond, wherein at least one of R ^2A is a hydroxyl group Further, at least one of R ^2A is an alkenyl group having 2 to 30 carbon atoms, and n ^A is synonymous with the above N. When n ^A is an integer of 2 or more, the structural formulas in n ^A [ ] may be the same or phase. X ^A represents an oxygen atom, a sulfur atom, a single bond or no crosslink, and m ^{2A is} independently an integer of 0 to 7, but at least one m ^2A is an integer of 2 to 7 or at least 2 m ^2A is 1~ An integer of 7, q ^{A is} independently 0 or 1.)

[4]

The compound represented by the above formula (1) is a compound described in [2] of the compound represented by the following formula (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 have the} same meanings as defined above, and R ⁶ to R ⁷ each independently may have a substituent. The alkyl group having 1 to 30 carbon atoms, the aryl group having 6 to 30 carbon atoms which may have a substituent, the alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and 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, and m ⁶ and m ^{7 are} each independently an integer of 0 to 7. , but m ⁴ , m ⁵ , m ⁶ and m ⁷ will not be 0 at the same time.)

[5]

The compound represented by the above formula (1-1) is a compound described in [4] of the compound represented by the following formula (1-2).

(In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ^{7 are} synonymous with the above, and R ⁸ to R ⁹ are R ⁶ to R ^{7 are} synonymous, R ¹² to R ^{13 are} synonymous with R ¹⁰ to R ¹¹ , and m ⁸ and m ^{9 are} each independently an integer of 0 to 8, but m ⁶ , m ⁷ , m ⁸ and m ^{9 are} not Also 0.)

[6]

The compound represented by the above formula (2) is a compound described in [3] of the compound represented by the following formula (2-1).

(In the formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^{A have the} same meanings as defined above, and each of R ^{3A is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have a substituent. An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group, wherein at least one of R ^3A is The alkenyl group having 2 to 30 carbon atoms, each of R ^{4A is} independently a hydrogen atom, and m ^{6A is} independently an integer of 0 to 5.

[7]

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

[8]

The resin described in [7] having the structure represented by the following formula (3).

(In the formula (3), L is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and a aryl group having 6 to 30 carbon atoms which may have a substituent. a substituent having 1 to 30 carbon atoms or a single bond, and the alkylene group, the above-mentioned extended aryl group and the aforementioned alkoxy group may have an ether bond, a ketone bond or an ester bond, and R ⁰ and the aforementioned R ^Y Synonymous, R ¹ is an N-valent or a single bond having 1 to 60 carbon atoms, and each of R ² to R ^{5 is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and a carbon number 6 to 30 which may have a substituent. An aryl group, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl group, the alkenyl group and the alkoxy group may contain an ether bond, ketone bond or an ester bond, wherein, R 1 at least ² ~ R ⁵ is a hydroxyl group, and R ² ~ R ⁵ is At least one of the alkenyl groups having 2 to 30 carbon atoms, m ² and m ^{3 are} each independently an integer of 0 to 8, and m ⁴ and m ^{5 are} each independently an integer of 0 to 9, but m ² , m ³ , m ⁴ and m ⁵ is not simultaneously ^{0, m 2, m 3,} m 4 and m ⁵ is an integer of at least 1 or m ^2, m ^{3 2} ~ 8 ~ 9 or 2, m ⁴ m ⁵ is an integer of at least 2 to 8 or 1 1 to 9)

[9]

The resin described in [7] having the structure represented by the following formula (4).

(In the formula (4), L is a linear or branched alkyl or single bond having 1 to 30 carbon atoms, R ^{0A is} synonymous with the above R ^Y , and R ^1A is an n ^A having a carbon number of 1 to 30. Or a single bond, each of R ^{2A is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an alkenyl group having 2 to 30 carbon atoms which may have a substituent Alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group which may have a substituent, the above alkyl group, the above aryl group, the aforementioned alkenyl group and the aforementioned alkane The oxy 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, and n ^A is synonymous 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 no cross-linking, and m ^{2A are} each independently 0 to 7. An integer, but at least one m ^2A is an integer from 2 to 7 or at least two m ^2A are integers from 1 to 7, and q ^{A is} independently 0 or 1.

[10]

One or more compositions selected from the group consisting of the compound according to any one of [1] to [6] and the resin according to any one of [7] to [9].

[11]

Further, the composition described in [10] of the solvent is contained.

[12]

Further, the composition described in [10] or [11] of the acid generator is further contained.

[13]

Further, the composition according to any one of [10] to [12] which contains a crosslinking agent.

[14]

The crosslinking agent is selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, a melamine compound, a guanamine compound, an ethylene glycol urea compound, a urea compound, an isocyanate compound, and an azide. At least one of the compositions described in [13] in which the compound compounds are grouped.

[15]

The crosslinking agent has a composition described in [13] or [14] of at least one allyl group.

[16]

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

[17]

Further, the composition according to any one of [13] to 16] which contains a crosslinking accelerator.

[18]

The crosslinking accelerator is a composition described in [17] selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.

[19]

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

[20]

Further, the composition according to any one of [10] to [19], which contains a radical polymerization initiator.

[twenty one]

The radical polymerization initiator is at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peracid polymerization initiator, and an azo polymerization initiator [10]~[20] The composition described in any one of them.

[twenty two]

The content of the radical polymerization initiator is from 0.05 to 25% by mass of the total mass of the solid component [10] to [21].

[twenty three]

A composition according to any one of [10] to [22] which is formed by using a film for lithography.

[twenty four]

The composition according to any one of [10] to [22] which is used for the formation of a resistive permanent film.

[25]

The composition according to any one of [10] to [22] which is formed by using an optical component.

[26]

A resist pattern forming method in which a photoresist layer is formed on the substrate using the composition described in [23], and radiation is irradiated in a predetermined region of the photoresist layer to perform development.

[27]

The step of forming a lower layer film on the substrate using the composition described in [23], forming at least one photoresist layer on the underlayer film, and irradiating radiation in a predetermined region of the photoresist layer to perform development A pattern of resist pattern formation.

[28]

The underlayer film is formed on the substrate by using the composition described in [23], and an intermediate layer film is formed on the underlayer film using a resist interlayer film material, and at least one photoresist layer is formed on the interlayer film. Thereafter, radiation is irradiated in a predetermined region of the photoresist layer, and after forming a resist pattern, the resist pattern is used as a mask, and the intermediate layer film is etched, and the obtained interlayer film is obtained. The pattern is a circuit pattern forming method in which the underlying film is etched as an etching mask, and the obtained underlying film pattern is used as an etching mask to etch the substrate, and then the pattern is formed on the substrate.

The compound and the resin in the present invention have high solubility in a safe solvent and have good heat resistance and etching resistance. Further, the resist composition containing the compound and/or resin of the present invention can impart a good resist pattern shape.

 [Formation of the Invention]  

Hereinafter, the form in which the present invention is to be carried out (hereinafter also referred to as "this embodiment") will be described. Further, 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 applicable to a wet process, and are useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance. Further, since the composition of the present embodiment is a compound or a resin having a specific structure by using heat resistance and high solvent solubility, it is possible to form a film which can suppress deterioration of the film during high-temperature baking, and also has excellent etching for oxygen plasma etching or the like. Resistant anti-corrosion and underlayer film. Further, when the underlayer film is formed, it is excellent in adhesion to the resist layer, so that an excellent resist pattern can be formed.

Further, since the coloring is high because of the high refractive index and the heat treatment from a wide range of temperatures from low temperature to high temperature is suppressed, it is also useful as various optical forming compositions.

 [Compound represented by formula (0)]  

The compound in the present embodiment is 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 of R ^{T is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have The aryl group having 6 to 30 carbon atoms of the substituent, the alkenyl group having 2 to 30 carbon atoms which may have a substituent, the alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, wherein the alkyl group, the aryl group, the above 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 R At least one of ^T is an alkenyl group having 2 to 30 carbon atoms, X represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, and m is independently an integer of 0 to 9, wherein at least one of m is 2~ An integer of 9 or at least two of m is an integer of 1 to 9, and N is an integer of 1 to 4. When N is an integer of 2 or more, the structural formulae of N [ ] may be the same or different, r Each is an integer from 0 to 2)

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

R ^z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of the aromatic rings is bonded via the R ^z . N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulae of N [ ] may be the same or different. Further, the N-valent group is an alkyl group having 1 to 60 carbon atoms when N=1, an alkylene group having 1 to 30 carbon atoms when N=2, and an alkane having 2 to 60 carbon atoms when N=3. The propyl group, when N=4, is an alkane tetra group having a carbon number of 3 to 60. Examples of the N-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Among them, the alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the N-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms.

R ^{T is} each independently 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, and may have a substitution. The alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group; the above alkyl group, the above aryl group, the above alkenyl group, and the above alkoxy group may contain an ether. A 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. Further, the alkyl group, the alkenyl group and the alkoxy group may be a linear chain, a branched chain or a cyclic group.

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

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

 [Compound represented by formula (1)]  

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

In the above formula (1), R ^{0 is} synonymous with the above R ^Y and is a hydrogen atom. When R ⁰ is a hydrogen atom, heat resistance is relatively high, and there is a tendency to improve solvent solubility.

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 are} each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an alkenyl group having 2 to 30 carbon atoms which may have a substituent. The alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the above alkyl group, the above aryl group, the above alkenyl group and the above alkoxy group may contain an ether bond, ketone bond or an ester bond, wherein, R ² ~ R ⁵ at least one hydroxyl group, and R ² ~ R ⁵ at least one carbon alkenyl group having 2 to 30.

m ² and m ^{3 are} each independently an integer of 0 to 8, and m ⁴ and m ^{5 are} each independently an integer of 0 to 9. However, m ² , m ³ , m ⁴ and m ^{5 are} not simultaneously zero. 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 Integer.

n is synonymous with the above N to be an integer of 1 to 4. However, when n is an integer of 2 or more, the structural formulae in n [ ] may be the same or different.

p ² to p ^{5 are} each an integer of 0 to 2 which is synonymous with the above r.

Further, the alkyl group, the alkenyl group and the alkoxy group may be a linear, branched or cyclic group.

Further, the n-valent group is an alkyl group having 1 to 60 carbon atoms when n=1, an alkylene group having 1 to 30 carbon atoms when n=2, and an alkane having 2 to 60 carbon atoms when n=3. The propyl group, when n=4, represents an alkane tetra group having a carbon number of 3 to 60. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Among them, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Among them, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

The compound represented by the above formula (1) can be used under high-temperature barbecue conditions even if it has a relatively low molecular weight and has high heat resistance due to the rigidity of the structure. Further, it has three grades of carbon or four grades of carbon in the molecule, and the crystallinity is suppressed, and it can be applied as a film forming composition which 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, the resist formation composition for lithography containing the compound represented by the above formula (1) can be provided with a good resist pattern shape.

Moreover, since the comparative low molecular weight is low in viscosity, even if it is a substrate having a step (especially in a fine space or a hole pattern), it can be uniformly filled under the corner of the step, and the flatness of the film can be easily improved. As a result, the underlayer film forming composition for lithography using this has good embedding and planarization characteristics. Further, high etching resistance can be imparted by a compound having a comparative carbon concentration.

Further, since the aromatic density is high, the refractive index is high, and even if the coloring is suppressed by a wide range of heat treatment from a low temperature to a high temperature, it is also useful as a composition for forming various optical components. Among them, a compound having a carbon of 4 grade is preferable from the viewpoint of suppressing oxidative decomposition of the compound and suppressing coloration, and improving heat resistance and solvent solubility. As an optical component, it is a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast improving lens, etc.), a retardation film, and an electromagnetic wave, in addition to a film-like or sheet-like component. A film for shielding, a prism, an optical fiber, 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 are useful.

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

In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ have the same meanings as defined above, and R ⁶ to R ^{7 are} each independently a substituent which may have a substituent. An alkyl group having 1 to 30 carbon atoms, 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 amine 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, and m ⁶ and m ^{7 are} each independently an integer of 0 to 7. However, m ⁴ , m ⁵ , m ⁶ and m ⁷ will not be 0 at the same time.

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

In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ have the same meanings as defined above, and R ⁸ to R ^{9 are} as described above. R ⁶ to R ^{7 are} synonymous, R ¹² to R ^{13 are} synonymous with R ¹⁰ to R ¹¹ described above, and m ⁸ and m ^{9 are} each independently an integer of 0 to 8. However, m ⁶ , m ⁷ , m ⁸ and m ⁹ will not be 0 at the same time.

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

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

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

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

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

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

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

In the above formula (1c), R ⁰ , R ¹ , R ⁶ to R ¹³ , m ⁶ to m ⁹ and n are synonymous with those described in the above 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.

In the above formula (1c'), R ⁰ , R ¹ , R ⁶ to R ¹³ , m ⁶ to m ⁹ and n are synonymous with those described in the above formula (1-2).

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

In the above formula, as described X in the above formula (0) are synonymous, R ^{T 'and} R ^T is synonymous explained in the above formula (0), m each independently represents an integer of 0 to 9, wherein, m is at least one of 2 An integer of ~9 or at least two of m are integers of 1-9. Here, at least one of R ^{T '} is a hydroxyl group, and at least one of R ^T' is an alkenyl group having 2 to 30 carbon atoms.

Specific examples of the compound represented by the above formula (0) are further exemplified below, but are not limited to the compounds exemplified herein.

In the above formulas, X in the formula (0) as described by synonymous, R ^{Y ',} R ^Z' and R ^Y as explained in the above formula (0), R ^Z synonymous. And each of R ^{4A is} independently a hydrogen atom.

Specific examples of the compound represented by the above formula (1) are exemplified below, and the compound represented by the formula (1) is not limited to the compounds exemplified above.

Among the above compounds, R ² , R ³ , R ⁴ and R ⁵ have the same meanings as those described in the above 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.

However, at least one selected from the group consisting of R ² , R ³ , R ⁴ and R ⁵ is a hydroxyl group, and at least one selected from the group consisting of 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 are} not simultaneously 0.

The compound represented by the above formula (1) is further preferably a compound represented by the following formula (BiF-1) to (BiF-5) from the viewpoint of solubility in an organic solvent (in the specific example, R ¹⁰ ~ R ¹³ is synonymous with the above).

In the above formula (BiF-1) to (BiF-5), R ^{6 '} to R ^{9 ' are} each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, and a carbon number 6 which may have a substituent. An aryl group of ~30, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group, wherein at least one of R ^{6 '} to R ^{9 '} R ² to R ^{13 are the} same as those described in the above formula (1c).

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

Examples of R ¹⁴ include 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 decyl group, a decyl group, an undecyl group, a dodecyl group, and a triaconyl group. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, Norbornyl, adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tri Decenyloxy, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group.

Each of the above R ¹⁴ is illustrative of an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as those described in the above formula (1-2), and R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6 to 30. 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 or a thiol group.

Examples of R ¹⁵ include 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 decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, a trideceneoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

Each of R ¹⁵ described above contains an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

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

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

R ^{14 is} independently 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, or an alkyl group having 1 to 30 carbon atoms. An oxy group, a halogen atom or a thiol group, and m ^14' is an integer of 0 to 4.

Examples of R ¹⁴ include 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 decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthryl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecenyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

Each of the above R ¹⁴ examples may contain an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as those described in the above formula (1-2), and R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6 to 30. 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 or a thiol group.

Examples of R ¹⁵ include 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 decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthryl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecenyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

Each of R ¹⁵ described above contains an isomer. For example, the butyl group contains n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as those described in the above formula (1-2), and R ¹⁶ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6~. a divalent aryl group of 30 or a divalent alkenyl group having 2 to 30 carbon atoms.

Examples of R ¹⁶ include a methyl group, an ethyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a nonenyl group, and an undecene group. Alkenyl, dodecenyl, tridecenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, ring Decenyl, cycloundecenyl, cyclododecenyl, cyclodecenyl, divalent norbornyl, divalent adamantyl, divalent phenyl, divalent naphthyl, divalent quinone A group, a divalent pentaphenyl group, a divalent vinyl group, a divalent allyl group, and a divalent tridecenyl group.

Each of the above R ¹⁶ is exemplified to contain an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

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

Examples of R ¹⁴ include 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 decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthryl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecenyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

Each of the above R ¹⁴ examples contains an isomer. For example, the butyl group contains n-butyl, isobutyl, sec-butyl, tert-butyl.

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

The above compound is more preferably a compound shown below from the viewpoint of availability of a raw material.

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

From the viewpoint of availability of raw materials, the above formula is preferably as shown in the following structure, and a compound having a dibenzoxanthene skeleton is preferred from the viewpoint of heat resistance.

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

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

 [Method for Producing Compound of Formula (0)]  

The compound represented by the formula (0) in the present embodiment can be suitably synthesized by a known method, and the synthesis method is not particularly limited. The compound represented by the formula (0) is exemplified below by taking the compound represented by the formula (1) as an example.

For example, under normal pressure, a polyphenol compound is obtained by a polycondensation reaction with a corresponding aldehyde under an acid catalyst by a bisphenol, a bisphenol, or a bisphenol, and at least one phenol of the polyphenol compound is continued. After introducing an allyl group into the hydroxyl group, it can be obtained by heating to cause a Claisen transition. Further, it may be carried out under pressure as necessary.

The time point at which the allyl group is introduced may be introduced in the stage before and after the condensation reaction, or after the production of the resin described later.

Examples of the bisphenols include bisphenol, methyl bisphenol, and methoxybis naphthol, and are not limited thereto. These may be used alone or in combination of two or more. In the above, from the viewpoint of the stability of the raw material supply, it is preferred to use bisphenol.

Examples of the bis-naphthols include bisnaphthol, methyl bis naphthol, and methoxy bis naphthol, but are not limited thereto. These may be used alone or in combination of two or more. Among these, from the viewpoint of increasing the concentration of carbon atoms and improving heat resistance, it is preferred to use bisnaphthol.

Examples of the aldehydes include formaldehyde, trioxane, paraldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, and nitrate. Butbenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural, etc., but are not limited thereto. These may be used alone or in combination of two or more. Among these, benzaldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzene are also used from the viewpoint of imparting higher heat resistance. Formaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural are preferred. From the viewpoint of improving etching resistance, benzaldehyde and hydroxybenzaldehyde are used. , chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene formaldehyde, hydrazine formaldehyde, furfural good.

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

The acid catalyst used in the above reaction can be suitably selected from known ones, and is not particularly limited. As such an acid catalyst, an inorganic acid or an organic acid is widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, and adipic acid. Azelaic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalene Organic acids such as sulfonic acid and naphthalene disulfonic acid; Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; or solid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid The acid or the like is not particularly limited to these. In the above, from the viewpoint of production, it is preferable to use an organic acid or a solid acid, and it is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of obtaining ease of production or ease of handling. Further, the acid catalyst may be used singly or in combination of two or more. In addition, the amount of the acid catalyst to be used may be appropriately set in accordance with the type of the raw material and the catalyst to be used, and the reaction conditions may be appropriately adjusted, and it is not particularly limited, and it is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material.

In the above reaction, a reaction solvent can be used. The reaction solvent is not particularly limited as long as it can be used as a reaction between an aldehyde or a ketone and a bisphenol, a bis-naphthol or a diterpene glycol, and can be suitably selected from known ones. The reaction solvent may, for example, be water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or a mixed solvent thereof. Further, the solvent may be used alone or in combination of two or more.

In addition, the amount of the reaction solvent to be used may be appropriately set in accordance with the type of the raw material and the catalyst to be used, and the reaction conditions are not particularly limited, and it is preferably in the range of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material. . Further, the reaction temperature in the above reaction can be appropriately selected in accordance with the reactivity of the reaction raw material, and is not particularly limited, and is usually in the range of 10 to 200 °C.

In order to obtain a polyphenol compound, it is preferred to have a higher reaction temperature, and it is preferably in the range of 60 to 200 °C. Further, the reaction method can be appropriately selected from known methods, and is not particularly limited, and examples thereof include a method of incorporating bisphenols, bis-naphthols or diterpenediols, aldehydes or ketones, and a catalyst together. A method of dropping a bisphenol, a bis-naphthol or a diterpene glycol or an aldehyde or a ketone in the presence of a catalyst. After the completion of the polycondensation reaction, the separation of the obtained compound can be carried out according to a usual method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, the compound of the target substance can be isolated by using a general method such as increasing the temperature of the reaction vessel to 130 to 230 ° C and removing the volatile portion at a level of 1 to 50 mmHg. .

As a preferred reaction condition, for aldehydes 1 mole, 1 mole to excess amount of bisphenols, bisphthylphenols or biguanide diol, and 0.001 to 1 mole of acid catalyst, at atmospheric pressure The reaction can be carried out at a temperature of 50 to 150 ° C for 20 minutes to 100 hours.

After the end of the reaction, the object can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added thereto, and the reaction product is precipitated. After cooling to room temperature, the mixture is filtered and separated, and the obtained solid is filtered and dried, and then separated and purified by column chromatography and by-products. The solvent is distilled off, filtered, and dried to obtain a compound represented by the above formula (1).

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

The compound used for the 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 particularly limited thereto.

First, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Continue to react in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide at normal pressure at 20 to 150 ° C for 6 to 72 hours. The reaction solution is neutralized with an acid, and the white solid added by the distilled water is precipitated, and the separated solid is washed with distilled water, or the solvent is evaporated and dried, and if necessary, washed with distilled water and dried to obtain a hydroxyl group. The hydrogen atom is a compound substituted with an allyl group.

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

In the present embodiment, the allyl group is reacted in the presence of a radical or an acid/base, and the solubility in the coating solvent or the acid, alkali or organic solvent used in the developing solution changes. The group substituted by the above allyl group is preferably formed by a pattern having a higher sensitivity and a high resolution, and is preferably a property of causing a chain reaction in the presence of a radical or an acid/base.

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

The resin obtained by using the compound represented by the above formula (1) as a monomer may, for example, be a structure having the following formula (3). In other words, the composition of the present embodiment may contain a resin having a structure represented by the following formula (3).

In the formula (3), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent. The alkoxy group or a single bond, the above alkylene group, the above-mentioned extended aryl group, and the above alkoxy group may contain an ether bond, a ketone bond or an ester bond. Further, the alkylene group and the alkylene group may be a linear, branched or cyclic group.

R ⁰ , R ¹ , R ² to R ⁵ , m ² and m ³ , m ⁴ and m ⁵ , p ² to p ⁵ and n are synonymous with those in the above formula (1).

However, m ² , m ³ , m ⁴ and m ^{5 are} not simultaneously 0, 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 or m ^{3 .} , ^{m. 4} and m ⁵ is at least two integer of 1 to 8 or 1 to 9, R ² ~ R ⁵ at least one is a hydroxyl group, and R ² ~ R ⁵ at least one of carbon atoms, alkenyl having 2 to 30 base.

 [Method for Producing Resin Obtained by Using Compound of Formula (1) as Monomer]  

The resin in the present embodiment is obtained by reacting a compound represented by the above formula (1) with a compound having crosslinking reactivity. The compound having the crosslinking reaction property may be obtained by oligomerizing or polymerizing the compound represented by the above formula (1), and a known one may be used without particular limitation. Specific examples of the aldehyde, a ketone, a carboxylic acid, a carboxylic acid halide, a halogen-containing compound, an amine compound, an imine compound, an isocyanate, and an unsaturated hydrocarbon group-containing compound are exemplified, but are not limited thereto.

Specific examples of the resin having a structure represented by the above formula (3) include, for example, a condensation reaction of an aldehyde and/or a ketone of a compound having a crosslinking reactivity with a compound represented by the above formula (1). Its phenolic varnished resin.

In addition, examples of the aldehyde used when the compound represented by the above formula (1) is subjected to novolak-forming include formaldehyde, trioxane, paraldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, and phenyl b. Aldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, The formaldehyde, furfural, and the like are not particularly limited thereto. The ketones are exemplified as the ketone. Among them, formaldehyde is preferred. Further, these aldehydes and/or ketones may be used alone or in combination of two or more. Further, the amount of the aldehyde and/or ketone used is not particularly limited, and the compound 1 represented by the above formula (1) is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles.

An acid catalyst can also be used for the condensation reaction of the compound represented by the above formula (1) with an aldehyde and/or a ketone. The acid catalyst to be used therein may be appropriately selected from those known in the art, and is not particularly limited. As such an acid catalyst, inorganic acids or organic acids are widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, and adipic acid; Azelaic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalene Organic acids such as sulfonic acid and naphthalene disulfonic acid; Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride or solid acid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid Etc., but it is not particularly limited to this. Among these, from the viewpoint of production, organic acid and solid acid are preferred, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of availability, ease of handling, and the like. Further, the acid catalyst may be used singly or in combination of two or more.

In addition, the amount of the acid catalyst to be used may be appropriately set depending on the type of the raw material and the catalyst to be used, and the reaction conditions are not particularly limited, and it is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material. However, with hydrazine, hydroxy hydrazine, benzofuran, hydroxy hydrazine, decene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, borneadiene When a copolymerization reaction of a compound of a non-conjugated double bond such as 5-vinylnorborn-2-ene, α-pinene, β-pinene or limonene is carried out, an aldehyde is not essential.

A reaction solvent can be used for the condensation reaction of the compound represented by the above formula (1) with an aldehyde and/or a ketone. The reaction solvent in the polycondensation is suitably selected from known ones, and is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixed solvent thereof. Further, the solvent may be used singly or in combination of two or more.

In addition, the amount of the solvent to be used may be appropriately set depending on the reaction conditions and the like, and is not particularly limited, but it is in the range of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material. good. Further, the reaction temperature is appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 °C. Further, the reaction method can be appropriately selected from known methods, and is not particularly limited. However, a method of adding the compound represented by the above formula (1), an aldehyde and/or a ketone, a catalyst, or the above formula (1) may be mentioned. A method in which a compound or an aldehyde and/or a ketone is added dropwise in the presence of a catalyst.

After the completion of the polycondensation reaction, the separation of the obtained compound can be carried out according to a usual method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, the object can be separated by a general method such as increasing the temperature of the reaction vessel to 130 to 230 ° C and removing the volatile portion at a level of 1 to 50 mmHg. A phenolic varnished resin.

Among them, the resin having the structure represented by the above formula (3) may be a single polymer of the compound represented by the above formula (1), or may be a copolymer with other phenols. Among them, examples of the phenol which can be copolymerized include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthol, and resorcin. Methyl resorcinol, catechol, butyl catechol, methoxy phenol, methoxy phenol, propyl phenol, pyrogallol, thymol, etc., are not particularly limited thereto. .

Further, the resin having the structure represented by the above formula (3) may be copolymerized with a polymerizable monomer in addition to the above other phenols. Examples of the copolymerizable monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, anthracene, hydroxyanthracene, benzofuran, hydroxyanthracene, decene, biphenylyl, and bisphenol. Further, triol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, norbornadiene, vinyl norbornene, decene, limonene or the like is not particularly limited. Further, even if the resin having the structure represented by the above formula (3) is a copolymer of two or more (for example, two to four elements) of the compound represented by the above formula (1) and the above phenol, even if it is a compound of the above formula (1) The copolymer of the compound and the above-mentioned copolymerized monomer of 2 or more (for example, 2 to 4 member) is a compound of the above formula (1) and the above phenol and the above-mentioned copolymerized monomer are 3 or more (for example, 3) ~4 element system) copolymer can also be.

The molecular weight of the resin having the structure represented by the above formula (3) is not particularly limited, and the weight average molecular weight (Mw) in terms of polystyrene is preferably from 500 to 30,000, preferably from 750 to 20,000. Moreover, the resin having the structure represented by the above formula (3) has a degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of 1.2 to 7 from the viewpoint of improving the crosslinking efficiency and suppressing the volatile component in the roasting. Those within the range are preferred. Further, the above Mw and Mn can be obtained by the method described in the examples below.

The resin having the structure represented by the above formula (3) is preferred because it can be more easily applied to a wet process, and has a high solubility in a solvent. More specifically, when 1-methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) is used as the solvent, the solubility of the solvent is preferably 10% by mass or more. The solubility of PGME and/or PGMEA is defined as "resin mass ÷ (resin mass + solvent mass) × 100 (% by mass)". For example, when 10 g of the resin is dissolved in PGMEA 90 g, the solubility of the resin to PGMEA is "10% by mass or more", and when it is not dissolved, it is "less than 10% by mass".

 [Compound represented by formula (2)]  

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

In the formula (2), R ^{0A is} synonymous with the above 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, and each of R ^{2A is} independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have a substitution. An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxyl group acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl group, the above alkenyl group and the alkoxy group may contain an ether bond, ketone or ester linkages, wherein, at least one of R ^2A is hydroxy, and R ^2A At least one of them is an alkenyl group having 2 to 30 carbon atoms.

n ^A is synonymous with 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 in n ^A [ ] may be the same or different.

X ^A each independently represents an oxygen atom, a sulfur atom, a single bond or no crosslinking. Among them, since X ^A tends to exhibit excellent heat resistance, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is preferred. From the viewpoint of solubility, X ^A is preferably a non-crosslinker.

m ^{2A are} each independently an integer of 0-6. However, at least one m ^2A is an integer of 2 to 6 or at least 2 of m ^2A is an integer of 1 to 6.

q ^{A is} independently 0 or 1.

Further, the above-mentioned n-valent group, when n=1, represents an alkyl group having 1 to 60 carbon atoms, when n=2, it represents an alkylene group having 1 to 30 carbon atoms, and when n=3, it represents a carbon number of 2 to 60. The alkane propyl group, when n = 4, represents an alkane tetra group having a carbon number of 3 to 60. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Among them, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the above n-valent group may have an aromatic group having 6 to 60 carbon atoms.

Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Among them, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

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

The compound represented by the above formula (2) can be used in a high-temperature barbecue condition even if it has a relatively low molecular weight and has high heat resistance due to the rigidity of the structure. Further, it has three grades of carbon or four grades of carbon in the molecule, and the crystallinity is suppressed, and it can be used as a composition for forming a film for lithography for use in film production for lithography.

Moreover, since the solubility in a safe solvent is high, heat resistance and etching resistance are good, and the resist formation composition for lithography containing the compound represented by the above formula (2) can be provided with a good resist pattern shape.

Moreover, since the relatively low molecular weight has a low viscosity, even if it is a substrate having a step (especially in a fine space or a hole pattern), it can be uniformly filled under the corner of the step, and the flatness of the film can be easily improved. The underlayer film forming composition for lithography using this has good embedding and planarization characteristics. Further, high etching resistance can be imparted by a compound having a comparative carbon concentration.

Further, since the aromatic density is high, the refractive index is high, and since coloring can be suppressed by a wide range of heat treatment from low temperature to high temperature, it is also useful as a composition for forming various optical components. Among them, a compound having a carbon of 4 grade is preferable from the viewpoint of suppressing oxidative decomposition of the compound to suppress coloration and improving heat resistance and solvent solubility. As an optical component, it is a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast-enhancing lens, etc.), a retardation film, and an electromagnetic wave shield in addition to a film-like or sheet-like component. It is useful for a film, a prism, an optical fiber, a solder resist for a flexible printed wiring, an electroplating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

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

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

R ^3A may have a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 2 2 The alkenyl group, halogen atom, nitro group, amine group, carboxylic acid group or thiol group of 30 may be the same or different for the same naphthalene ring or benzene ring. ^Here , at least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms, R ^{4A is} each independently a hydrogen atom, and m ^{6A is} independently an integer of 0 to 5.

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

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

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

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

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

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

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

The compound represented by the above formula (2) is further represented by the following formula (BisN-1) to (BisN-4) or (XBisN-1) to (XBisN-3) from the viewpoint of solubility in an organic solvent. It is excellent.

In the above formulae (BisN-1) to (BisN-4) and (XBisN-1) to (XBisN-3), R ^3A and R ^4A have the same meanings as those described in the above formula (2-1). However, at least one of R ^3A is an alkenyl group having 2 to 30 carbon atoms.

 [Method for Producing Compound of Formula (2)]  

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

For example, under normal pressure, a polyphenol compound is obtained by performing a polycondensation reaction of a phenol or a naphthol with a corresponding aldehyde or a ketone under an acid catalyst, and continuing at least one phenolic hydroxyl group of the polyphenol compound. After the allyl group is introduced, it is obtained by transferring Claisen by heating. Further, it can be carried out under pressure as necessary.

The time point at which the allyl group is introduced can be introduced after the production of the resin described later in the step, the subsequent stage or the later stage of the condensation reaction.

The naphthol is not particularly limited, and examples thereof include naphthol, methylnaphthol, methoxynaphthol, and naphthalenediol. Among them, naphthalene is also used from the viewpoint of easily producing a xanthene structure. Alcohol is preferred.

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

Examples of the aldehydes include formaldehyde, trioxane, paraldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, and nitrate. The benzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural, and the like are not particularly limited thereto. These can be used individually or in combination of 2 or more types. They also use benzaldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethylbenzene from the viewpoint of imparting high heat resistance. Formaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural are preferred. From the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, Chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural are preferred .

The acid catalyst used in the above reaction can be suitably selected from those known in the art, and is not particularly limited. The acid catalyst may be suitably selected from known inorganic acids and organic acids, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid; Organic acids such as acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalene disulfonic acid; Lewis acid such as zinc chloride, aluminum chloride, ferric chloride, boron trifluoride; A solid acid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid. Among them, hydrochloric acid or sulfuric acid is preferred from the viewpoint of ease of production, ease of handling, and the like. The acid catalyst may be used alone or in combination of two or more.

A reaction solvent can be used in the above reaction. The reaction solvent is not particularly limited as long as it can be reacted with an aldehyde or a ketone or a naphthol, and for example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran or dioxane can be used. Or these mixed solvents. The amount of the reaction solvent is not particularly limited, and is, for example, in the range of 0 to 2000 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 in accordance with the reactivity of the reaction raw material, but it is preferably in the range of 10 to 200 °C. In the present embodiment, from the viewpoint of selectively synthesizing the compound represented by the formula (2), those having a lower temperature are preferred, and those having a temperature of from 10 to 60 ° C are preferred.

The reaction method is not particularly limited, and examples thereof include a method in which a naphthol or the like, an aldehyde or a ketone, a catalyst, or a method in which a naphthol or an aldehyde is dropped in the presence of a catalyst. After the end of the polycondensation reaction, the unreacted raw material or catalyst which is present in the system is removed, and the temperature of the reaction vessel can be raised to 130 to 230 ° C to remove volatile components at a level of 1 to 50 mmHg.

The amount of the raw material is not particularly limited. For example, for the aldehyde 1 mole, 2 moles to excess amount such as naphthol and 0.001 to 1 mole of acid catalyst are used, and 20 minutes at 20 to 60 ° C under normal pressure. Responders of ~100 hours are preferred.

After the reaction is completed, the object is separated by a known method. The method for separating the target product is not particularly limited. For example, a concentrated reaction liquid is added, pure water is added thereto, and the reaction product is precipitated. After cooling to room temperature, the mixture is filtered and separated, and the obtained solid is filtered, and dried. The column chromatography and the by-product are separated and purified, and the solvent is distilled off, filtered, and dried to separate the objective compound.

Further, a method of introducing an allyl group to at least one phenolic hydroxyl group of the polyphenol compound is also known.

For example, as shown below, an allyl group can be introduced into the phenolic hydroxyl group of at least one of the above compounds.

The compound to be introduced into the allyl group can be synthesized or can be easily obtained by a known method, and examples thereof include allyl chloride, allylic propyl bromide and allyl iodide, but are not particularly limited thereto.

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

In the present embodiment, the allyl group is reacted in the presence of a radical or an acid/base, and the solubility in the coating solvent or the acid, alkali or organic solvent used in the developing solution changes. The above-mentioned group substituted with an allyl group is more likely to form a pattern having high sensitivity and high resolution, and it is preferable to have a property of causing a chain reaction in the presence of a radical or an acid/base.

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

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

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

The resin obtained by using the compound represented by the above formula (2) as a monomer may, for example, be a structure having the following formula (4). In other words, the composition in the present embodiment may be a resin containing a structure having the structure represented by the following formula (4).

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

R ^0A , R ^1A , R ^2A , m ^2A , n ^A , q ^A and X ^A are synonymous with the above formula (2), but when n ^A is an integer of 2 or more, n ^A structural formulas in [ ] The same or different, at least one m ^2A is an integer of 2-6 or at least two m ^2A is an integer of 1-6, at least one of R ^2A is a hydroxyl group, and at least one carbon is 2-30. Alkenyl.

 [Method for Producing Resin Obtained by Using Compound of Formula (2) as Monomer]  

The resin in the present embodiment can be obtained by reacting a compound represented by the above formula (2) with a compound having crosslinking reactivity. The compound having cross-linking reactivity may be obtained by merely oligomerizing or polymerizing the compound represented by the above formula (2), and is not particularly limited as long as it is known to the public. Examples of the specific examples include an aldehyde, a ketone, a carboxylic acid, a carboxylic acid halide, a halogen-containing compound, an amine compound, an imine compound, an isocyanate, and an unsaturated hydrocarbon group-containing compound. However, the compound is not particularly limited thereto. .

Specific examples of the resin having a structure represented by the above formula (4) include a condensation reaction of a compound represented by the above formula (2) with an aldehyde having an crosslinking reactivity, and/or a ketone. A novolak-refined resin.

In addition, examples of the aldehyde used when the compound represented by the above formula (2) is used for novolak formation include formaldehyde, trioxane, paraldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, and phenyl acetaldehyde. , phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene, hydrazine Formaldehyde, furfural, etc., but it is not specifically limited to these. Examples of the ketone include the above ketones. Formaldehyde is also preferred in these. Further, these aldehydes and/or ketones may be used alone or in combination of two or more. Further, the amount of the aldehyde and/or ketone used is not particularly limited, but the compound 1 represented by the above formula (2) is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles.

An acid catalyst can be used for the condensation reaction of the compound represented by the above formula (2) with an aldehyde and/or a ketone. The acid catalyst used therein may be appropriately selected from those known from the public, but is not particularly limited. As such an acid catalyst, an inorganic acid or an organic acid is widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, adipic acid, and hydrazine. Acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid An organic acid such as naphthalene disulfonic acid; a solid acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; or a solid acid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid; However, it is not particularly limited to this. Among them, from the viewpoint of production, an organic acid or a solid acid is preferred, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of availability, ease of handling, and the like. Further, the acid catalyst may be used singly or in combination of two or more.

In addition, the amount of the acid catalyst to be used may be appropriately set in accordance with the reaction conditions and the like, and is not particularly limited. However, the amount of the reaction raw material is 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material. It is better. But in combination with hydrazine, hydroxy hydrazine, benzofuran, hydroxy hydrazine, decene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, borneol, When a copolymerization reaction of a compound having a non-conjugated double bond such as 5-vinylnorborn-2-ene, α-pinene, β-pinene or limonene is carried out, an aldehyde is not essential.

A reaction solvent can be used for the condensation reaction of the compound represented by the above formula (2) with an aldehyde and/or a ketone. The reaction solvent in the polycondensation is suitably selected from known ones, and is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixed solvent thereof. Further, the solvent may be used singly or in combination of two or more.

In addition, the amount of the solvent to be used may be appropriately set in accordance with the reaction materials and the like, and is not particularly limited, and is in the range of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material. It is better. Further, the reaction temperature is appropriately selected in accordance with the reactivity of the reaction raw material, and is not particularly limited, and is usually in the range of 10 to 200 °C. Further, the reaction method can be appropriately selected from known methods, and is not particularly limited, and a method of incorporating the compound represented by the above formula (2), an aldehyde and/or a ketone, a catalyst, or the above formula ( 2) A method of dropping the compound or aldehyde and/or ketone shown in the presence of a catalyst.

After the completion of the polycondensation reaction, the separation of the obtained compound can be carried out according to a usual method, but is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, a general method such as removing volatile components at a temperature of from 1 to 50 mmHg can be carried out by raising the temperature of the reaction vessel to 130 to 230 ° C to separate the target phenol varnish. Resin.

Among them, the resin having the structure represented by the above formula (4) may be a single polymer of the compound represented by the above formula (2), but may be a copolymer with other phenols. In addition, examples of the phenol which can be copolymerized include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthol, and resorcinol. Methyl resorcinol, catechol, butyl catechol, methoxy phenol, methoxy phenol, propyl phenol, pyrogallol, thymol, etc., but is not particularly limited thereto Wait.

Further, the resin having the structure represented by the above formula (4) may be copolymerized with a polymerizable monomer in addition to the above other phenols. Examples of the copolymerizable monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, anthracene, hydroxyanthracene, benzofuran, hydroxyanthracene, decene, biphenylyl, and bisphenol. And tris, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, borneol, vinyl norbornene, decene, limonene, etc., but are not particularly limited thereto. Further, the resin having the structure represented by the above formula (4) is a compound of the above formula (2) and a copolymer of two or more (for example, two to four elements) of the above phenol, even if it is the above formula (2) The copolymer of 2 or more (for example, 2 to 4 member) of the above-mentioned copolymerized monomer is a compound of the above formula (2) and a ternary or higher amount of the above-mentioned phenol and the above-mentioned copolymerized monomer ( For example, a 3 to 4 member copolymer) may also be used.

Further, the molecular weight of the resin having the structure represented by the above formula (4) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably from 500 to 30,000, preferably from 750 to 20,000. Moreover, the degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the resin having the structure represented by the above formula (4) is 1.2 to 7 from the viewpoint of suppressing the crosslinking component while improving the crosslinking efficiency. The range is better. Further, the above Mw and Mn can be obtained by the method described in the examples below.

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

 [Purification method of compound and / or resin]  

The method for purifying the compound and/or the resin in the present embodiment contains at least one of a resin selected from the group consisting of the compound represented by the above formula (0) or the compound represented by the above formula (0) as a monomer. More specifically, the compound represented by the above formula (1), the resin obtained by using the compound represented by the above formula (1) as a monomer, the compound represented by the above formula (2), and the compound represented by the above formula (2) as a single a step of obtaining a solution (S) by dissolving one or more kinds of the obtained resin in a solvent, contacting the obtained solution (S) with an acidic aqueous solution, and extracting impurities in the above compound and/or the above resin (first extraction step) The solvent used in the step of obtaining the above solution (S) contains a solvent which is not arbitrarily mixed with water.

In the first extraction step, the resin is preferably a resin obtained by reacting a compound represented by the above formula (1) and/or a compound represented by the formula (2) with a compound having crosslinking reactivity. The purification method of the present embodiment can reduce the content of various metals contained as impurities in the compound or resin having the above specific structure.

More specifically, in the purification method of the present embodiment, the above compound and/or the above resin is dissolved in an organic solvent which is not arbitrarily mixed with water to obtain a solution (S), and the solution (S) can be further contacted with an acidic aqueous solution. After the extraction treatment. Thereby, after the metal portion contained in the above 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 singly or in combination of two or more kinds. Further, the above compound or resin may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers, and the like.

The solvent which is used in the purification method of the present embodiment and which is not arbitrarily mixed with water is not particularly limited, and is preferably an organic solvent which can be safely applied in a semiconductor manufacturing process, specifically, water at room temperature. The solubility is less than 30%, preferably less than 20%, more preferably less than 10% organic solvent. The amount of the organic solvent used is preferably from 1 to 100 times by mass based on the total amount of the compound to be used and the resin.

Specific examples of the solvent which is not arbitrarily mixed with water are not limited to the following, and examples thereof include ethers such as diethyl ether and diisopropyl ether; ethyl acetate, n-butyl acetate, and isoamyl acetate; Ketones such as esters, esters such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; Glycol ether acetate such as ethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate; n-hexane An aliphatic hydrocarbon such as n-heptane; an aromatic hydrocarbon such as toluene or xylene; or a halogenated hydrocarbon such as dichloromethane or chloroform. Among them, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate are preferred, and methyl isobutyl ketone is preferred. Ethyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate are preferred, and methyl isobutyl ketone or ethyl acetate is more preferred. Methyl isobutyl ketone, ethyl acetate, etc., because the above compound and the resin containing the compound as a constituent component have a relatively high saturated solubility and a relatively low boiling point, the step of distilling off the industrial solvent or removing it by drying can be reduced. The load. These solvents may be used alone or in combination of two or more.

The acidic aqueous solution used in the purification method of the present embodiment can be suitably selected from those in which an organic compound or an inorganic compound which is generally known is dissolved in an aqueous solution of water. The acidic aqueous solution is not limited to the ones described below, and examples thereof include an aqueous solution of an inorganic acid in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid is dissolved in water; acetic acid, propionic acid, oxalic acid, malonic acid, and succinic acid are used. An organic acid aqueous solution in which an organic acid such as fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid or trifluoroacetic acid is dissolved in water. These acidic aqueous solutions may be used singly or in combination of two or more. Among these acidic aqueous solutions, one or more inorganic acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are also selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, and Malay. It is preferred to use one or more kinds of organic acid aqueous solutions in the group of acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid, and sulfuric acid, nitric acid, and acetic acid, oxalic acid, tartaric acid, An aqueous solution of a carboxylic acid such as citric acid is preferred, and an aqueous solution of sulfuric acid, oxalic acid, tartaric acid or citric acid is more preferred, and an aqueous solution of oxalic acid is more preferred. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid are also known to be more effective in removing metals because they are coordinated to metal ions to produce a chelate effect. Further, the water used herein is preferably a water having a small metal content, for example, ion-exchanged water or the like, for the purpose of the purification method according to the present embodiment.

The pH of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, but the acidity of the aqueous solution is preferably adjusted in consideration of the influence on the above compound or resin. The pH of the acidic aqueous solution is usually from 0 to 5, preferably from 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, and the amount of use is adjusted from the viewpoint of reducing the number of extractions for which metal removal is required, and from the viewpoint of ensuring operability in consideration of the total amount of liquid. It is better. From the above viewpoints, the amount of the acidic aqueous solution used is preferably from 10 to 200% by mass, preferably from 20 to 100% by mass, based on 100% by mass of the solution (S).

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

In the purification method of the present embodiment, it is preferred that the solution (S) further contains an organic solvent which is optionally mixed with water. When the solution (S) contains an organic solvent which is optionally mixed with water, the amount of the compound and/or the resin to be added can be increased, and the liquid separation property can be improved, and the purification can be carried out under high autoclave efficiency. The method of adding an organic solvent arbitrarily mixed with water is not particularly limited, and examples thereof include a method of previously adding a solution containing an organic solvent, a method of previously adding to water or an acidic aqueous solution, a solution containing an organic solvent, and water or an acidic aqueous solution. Any of the methods of adding after contact may be used. Among these, a method of preliminarily adding a solution containing an organic solvent is preferred from the viewpoint of ease of management of handling workability and loading amount.

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

Specific examples of the organic solvent to be arbitrarily mixed with water used in the purification method of the present embodiment are not limited to the following, and examples thereof include ethers such as tetrahydrofuran and 1,3-difuran; and methanol, ethanol, and the like. Alcohols such as propanol; ketones such as acetone and N-methylpyrrolidone; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, etc. An aliphatic hydrocarbon such as a glycol ether. Among them, N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferred, and N-methylpyrrolidone and propylene glycol monomethyl ether are preferred. These solvents may be used singly or in combination of two or more.

The temperature at which the extraction treatment is carried out is usually 20 to 90 ° C, preferably 30 to 80 ° C. The extraction operation is carried out by standing still, for example, by stirring or the like. Thereby, the metal portion contained in the solution (S) is moved to the aqueous phase. Moreover, by this operation, the acidity of the solution is lowered, and 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 can be recovered by decantation or the like. The standing time is not particularly limited, and it is preferable to adjust the standing time from the viewpoint of more preferably separating the solvent phase and the aqueous phase. The standing time is usually 1 minute or longer, preferably 10 minutes or longer, preferably 30 minutes or longer. Further, the extraction treatment may be performed only once, but it is also effective to repeat the mixing, standing, and separation operations.

The purification method of the present embodiment is a step (second extraction step) in which the solution containing the compound or the resin is further contacted with water after the first extraction step, and the impurities in the compound or the resin are extracted. It is better. Specifically, for example, after the above-described extraction treatment using an acidic aqueous solution, it is preferred to further include a solution containing a compound and/or a resin extracted and recovered from the aqueous solution and a solvent, and further extracting the solution by water. The extraction treatment of the water is not particularly limited. For example, the solution phase and the water are sufficiently mixed by stirring or the like, and then the resulting mixed solution is allowed to stand. Since the mixed solution after the standing is separated into a solution phase containing a compound and/or a resin and a solvent, the solution phase can be recovered by decantation or the like.

Further, the water to be used therein is preferably a water having a small metal content, for example, ion-exchanged water or the like, for the purpose of the embodiment according to the present embodiment. The extraction treatment can be carried out only once, but it is also effective to repeat the operation of mixing, standing and separating several times. Moreover, the conditions of use, temperature, time, and the like of the two in the extraction treatment are not particularly limited as in the case of the above-described contact treatment with an acidic aqueous solution.

The water mixed in the solution containing the obtained compound and/or the resin and the solvent can be easily removed by an operation such as vacuum distillation. Further, the concentration of the compound and/or the resin may be adjusted to any concentration as necessary to add the solvent to the solution.

The method for separating the compound and/or the resin from the solution containing the obtained compound and/or the resin and the solvent is not particularly limited, and a known method such as removal under reduced pressure, separation by reprecipitation, and combinations thereof may be employed. A known treatment such as a concentration operation, a filtration operation, a centrifugal separation operation, and a drying operation may be performed as necessary.

 [composition]  

The composition in the present embodiment contains a resin selected from the group consisting of the compound represented by the above formula (0) and the compound represented by the above formula (0) as a monomer, and more specifically a compound represented by the above formula (1). a resin obtained by using the compound represented by the above formula (1) as a monomer, a compound represented by the above formula (2), a resin obtained by using the compound represented by the above formula (2) as a monomer, a solvent, an acid generator, and One or more of a group of a crosslinking agent, a crosslinking accelerator, a radical polymerization initiator, and the like.

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

 [Film forming composition for lithography for chemical amplification type resist]  

The film forming composition for lithography (hereinafter also referred to as "resist composition") used in the chemical amplification type resist is contained in the present embodiment, and is selected from the compound represented by the above formula (0) and The resin obtained by using the compound represented by the above formula (0) as a monomer is more specifically a compound represented by the above formula (1), a resin obtained by using the compound represented by the above formula (1) as a monomer, and the above formula (2). One or more types of the compound obtained by using the compound represented by the above formula (2) as a monomer are used as a resist substrate.

Further, the composition (resist composition) in the present embodiment is preferably a solvent. The solvent is not particularly limited, and examples thereof include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol. Ethylene glycol monoalkyl ether acetate such as alcohol mono-n-butyl ether acetate; ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; propylene glycol single Propylene glycol monoalkyl ether acetate such as methyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, etc. Lactic acid esters; aliphatic carboxylic acids such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate Esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxy-2 -methyl methacrylate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Acetate, butyl 3-methoxy-3-methylpropanoate, butyl 3-methoxy-3-methylbutyrate, methyl ethyl acetate, methyl pyruvate, ethyl pyruvate Other esters; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN); N, N-dimethylformamide, N-methylacetamide, phthalamide such as N,N-dimethylacetamide or N-methylpyrrolidone; lactones such as γ-lactone, etc. However, it is not particularly limited to this. These solvents may be used singly or in combination of two or more.

The solvent used in the present embodiment is preferably a safe solvent, and is preferably selected from the group consisting of PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate. At least one, more preferably at least one selected from the group consisting of PGMEA, PGME, and CHN.

In the present embodiment, the solid content and the amount of the solvent are not particularly limited, and the solid content is preferably from 1 to 80% by mass and the solvent is from 20 to 99% by mass based on 100% by mass of the total mass of the solvent. It is preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, more preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid component and 90% of the solvent. 98% by mass.

The resist composition of the present embodiment may contain, as other solid components, a group selected from the group consisting of an acid generator (C), a crosslinking agent (G), an acid diffusion controlling agent (E), and other components (F). At least one. Further, the "solid content" in the present specification means a component other than the solvent.

In addition, the acid generator (C), the crosslinking agent (G), the acid diffusion controlling agent (E), and other components (F) can be used, and it is not specifically limited, for example, International Publication No. 2013/024778 The record is better.

 [mixing ratio of each component]  

In the anticorrosive composition of the present embodiment, the content of the compound and/or the resin used as the resist substrate is not particularly limited, and the total mass of the solid component (including the resist substrate and the acid generator (C)) The total of the solid components of the arbitrarily used component such as the crosslinking agent (G), the acid diffusion controlling agent (E), and the other component (F) is preferably the same as the following: 50 to 99.4% by mass, preferably 55 to 90% by mass, more preferably 60 to 80% by mass, particularly preferably 60 to 70% by mass. When the content of the compound and/or the resin used as the resist base material is in the above range, the resolution can be further improved, and the line edge roughness (LER) progress tends to be small.

Further, when both the compound and the resin are contained as the resist substrate, the content is the total amount of the two components.

 [Other ingredients (F)]  

In the anticorrosive composition of the present embodiment, as a resist substrate, an acid generator (C), a crosslinking agent (G), and an acid diffusion controlling agent (E), if it does not inhibit the object of the present invention. The other components may be added with one or more kinds of dissolution promoters, dissolution control agents, sensitizers, surfactants, organic carboxylic acids or phosphorus oxyacids or derivatives thereof, heat and/or photohardenable touches. Medium, polymerization inhibiting agent, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, pigment, tackifier, slip agent, antifoaming agent, coating agent, ultraviolet absorber, interface Various additives such as an active agent, a colorant, and a nonionic surfactant. Further, for the present specification, the other component (F) may be referred to as an optional component (F).

In the resist composition of the present embodiment, a resist substrate (hereinafter also referred to as "component (A)"), an acid generator (C), a crosslinking agent (G), an acid diffusion controlling agent (E), or any The content of the component (F) (component (A) / acid generator (C) / crosslinking agent (G) / acid diffusion controlling agent (E) / optional component (F)) is based on the mass% of the solid matter Preferably, it is 50~99.4/0.001~49/0.5~49/0.001~49/0~49, preferably 55~90/1~40/0.5~40/0.01~10/0~5, more preferably 60~80/3~30/1~30/0.01~5/0~1, especially good 60~70/10~25/2~20/0.01~3/0.

The mixing ratio of each component is such that the total synthesis is 100% by mass, and is selected from the respective ranges. When the blending ratio of each component is in the above range, it tends to have excellent properties such as sensitivity, resolution, and development.

In the case of using the resist composition of the present embodiment, the components are dissolved in a solvent to form a homogeneous solution, and then, for example, a filter having a pore diameter of about 0.2 μm is used for filtration.

The resist composition of the present embodiment may contain a resin other than the resin of the present embodiment, within a range not inhibiting the object of the present invention. The other resin is not particularly limited, and examples thereof include novolac resin, polyvinyl phenol, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol or vinyl phenol as monomers. The polymer contained in the unit or these derivatives. The content of the other resin is not particularly limited, and may be appropriately adjusted depending on the type of the component (A) to be used. However, it is preferably 30 parts by mass or less, and preferably 10 parts by mass or less, based on 100 parts by mass of the component (A). More preferably, it is 5 parts by mass or less, and particularly preferably 0 parts by mass.

 [Physical properties of the resist composition, etc.]  

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. According to the compound represented by the above formula (1) and/or formula (2), the type of the resin obtained as a monomer and/or the type of the developing liquid used, it can be classified into a positive resist pattern and a negative type. Any of the resist patterns.

In the case of the positive resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment preferably has a dissolution rate of 5 Å/sec or less for the developing solution at 23 ° C, and is 0.05. It is better to use ~5Å/sec, and it is better to use 0.0005~5Å/sec. When the dissolution rate is 5 Å/sec or less, it is insoluble in the developing solution, and tends to be easily resisted. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution is improved. This is estimated by dissolving the solubility change before and after exposure of the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component in the exposure portion of the developing solution and dissolving it in the developing solution. The interface of the unexposed part is relatively large. Also, see the reduction of LER and the effect of reducing it.

In the case of the negative resist pattern, it is preferable that the amorphous film formed by spin coating the resist composition of the present embodiment has a dissolution rate of the developing solution at 23 ° C of 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is suitable for the resist. Moreover, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be caused by the dissolution of the micro surface portion of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component to reduce the LER. I also saw the effect of reducing the 瑕疵.

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

In the case of a positive resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment is exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. It is preferred that the dissolution rate of the developing solution is 10 Å/sec or more at 23 ° C. When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is suitable for the resist. Moreover, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be caused by the dissolution of the micro surface portion of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component to reduce the LER. I also saw the effect of reducing the 瑕疵.

In the case of a negative resist pattern, the amorphous film formed by spin coating of the resist composition of the present embodiment is exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The portion is preferably 5 Å/sec or less for the dissolution rate of the developing solution at 23 ° C, preferably 0.05 to 5 Å / sec, and more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å/sec or less, the developing solution is insoluble, and it tends to be easily used as a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. It is presumed that the change in solubility before and after exposure of the resin containing the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component is dissolved in the unexposed portion of the developing solution and is not dissolved in The contrast of the interface of the exposure portion of the developing liquid is increased. In addition, we also saw the reduction of LER and the effect of reducing it.

 [Film forming composition for lithography for non-chemical amplification type resist use]  

The component (A) of the composition for forming a film for lithography (hereinafter also referred to as "radiation-sensitive composition") used in the non-chemically amplified resist for use in the present embodiment, and the photoactivity of diazonaphthylquinone described later The compound (B) is used in combination as a positive type which is a compound which is easily dissolved in a developing solution by irradiating a g-line, an h-line, an i-line, a KrF excimer laser, an ArF excimer laser, an extreme ultraviolet ray, an electron beam or an X-ray. A substrate for resist is useful. By g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray, although the properties of component (A) do not change much, it is difficult for imaging liquid. The dissolved diazonaphthoquinone photoactive compound (B) becomes a compound which is easily dissolved, and a resist pattern can be produced by a developing step.

Since the component (A) contained in the radiation sensitive composition of the present embodiment has a relatively low molecular weight compound, the roughness of the obtained resist pattern is extremely small. Further, in the above formula (1), it is preferable to contain a group of at least one iodine atom selected from the group consisting of R ⁰ to R ⁵ , and in the above formula (2), it is selected from R ^0A , R ^1A and R ^It is preferred that at least one of the groups of ^2A is a group containing an iodine atom. When the radiation sensitive composition of the present embodiment is applied to the component (A) having a group containing an iodine atom, the absorption energy for radiation such as electron beams, extreme ultraviolet rays (EUV), and X-rays is increased, and as a result, the sensitivity can be improved. Better.

The glass transition temperature of the component (A) of the radiation sensitive composition of the present embodiment is preferably 100 ° C or higher, preferably 120 ° C or higher, more preferably 140 ° C or higher, and particularly preferably 150 ° C or higher. The upper limit of the glass transition temperature of the component (A) is not particularly limited and is, for example, 400 °C. When the glass transition temperature of the component (A) is within the above range, the semiconductor photolithography process has a tendency to maintain heat resistance in a pattern shape and to improve performance such as high resolution.

The crystallization heat amount obtained by differential scanning calorimetry of the glass transition temperature of the component (A) of the radiation sensitive composition of the present embodiment is preferably less than 20 J/g. Further, the crystallization temperature)-(glass transition temperature) is preferably 70 ° C or higher, preferably 80 ° C or higher, more preferably 100 ° C or higher, and particularly preferably 130 ° C or higher. When the crystallization heat generation amount is less than 20 J/g, or (crystallization temperature) - (glass transition temperature) is within the above range, the amorphous film is easily formed by spin-coating the radiation-sensitive composition, and is kept on the resist for a long period of time. The film forming property necessary for the above has a tendency to improve the resolution.

In the present embodiment, the crystallization heat generation amount, the crystallization temperature, and the glass transition temperature can be determined by differential scanning calorimetry using DSC/TA-50WS manufactured by Shimadzu Corporation. About 10 mg of the sample was placed in an unsealed container made of aluminum, and the temperature was raised to a melting point or higher at a temperature rising rate of 20 ° C /min in a nitrogen gas stream (50 mL / min). After quenching, the temperature was raised to a temperature above the melting point again at a temperature increase rate of 20 ° C / min in a nitrogen stream (30 mL / min). After quenching, the temperature was raised again to 400 ° C at a temperature increase rate of 20 ° C / min in a nitrogen stream (30 mL / min). The temperature at which the midpoint of the step line of the stepped line is changed (half the change to the specific heat) is taken as the glass transition temperature (Tg), and the temperature of the heat absorption peak appearing thereafter is taken as the crystallization temperature. The calorific value is obtained from the area of the region surrounding the heat absorption peak and the bottom line as the crystallization heat.

The component (A) contained in the radiation sensitive composition of the present embodiment is preferably 100 or less at normal pressure, preferably 120 ° C or lower, preferably 130 ° C or lower, more preferably 140 ° C or lower, and particularly preferably 150 ° C. Below, it is better because of lower sublimation. The sublimation property is low, and in the thermogravimetric analysis, the weight loss at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, preferably 3% or less, and more preferably 1% or less. It is 0.1% or less. By sublimation is low, contamination of the exposure device caused by air leakage during exposure can be prevented. Further, a pattern shape with a low roughness can be obtained.

The component (A) contained in the radiation sensitive composition of the present embodiment is selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), and cyclopentanone. (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate, and the highest solubility energy in the component (A), at 1 °C at 23 ° C More preferably, it is more than 5% by mass, more preferably 5% by mass or more, more preferably 10% by mass or more. It is particularly preferably selected from the group consisting of PGMEA, PGME, and CHN, and the solvent exhibiting the highest solubility in the (A) resist substrate is 20% by mass or more at 23° C., particularly preferably, for PGMEA at 23° C. Dissolved in an amount of 20% by mass or more. By satisfying the above conditions, the use of semiconductor manufacturing steps in actual production becomes easy.

 [Diazonaphthoquinone photoactive compound (B)]  

The diazo naphthoquinone photoactive compound (B) contained in the radiation sensitive composition of the present embodiment is a diazonaphthylquinone substance containing a polymerizable and non-polymeric diazonaphthoquinone photoactive compound, generally for positive The type of the anti-corrosive composition can be used as a photosensitive component (photosensitive agent), and it is not particularly limited, and one type or two or more types can be used arbitrarily.

As the component (B), a naphthoquinonediazide sulfonate chloride or a benzoquinonediazide sulfonate chloride or the like and a low molecule which can be subjected to a condensation reaction with these acid chlorides A compound obtained by reacting a compound or a polymer compound is preferred. In particular, the functional group which can be condensed with the acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amine group, and particularly preferably a hydroxyl group. The compound which can be condensed with the acid chloride containing a hydroxyl group is not particularly limited, and examples thereof include hydroquinone, resorcin, 2, 4-dihydroxybenzophenone, and 2,3,4-trihydroxyl group. Benzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2 2', 4, 4'-tetrahydroxybenzophenone, 2, 2', 3, 4, 6'-pentahydroxybenzophenone and other hydroxybenzophenones; bis (2, 4-dihydroxybenzene) Hydroxyphenyl alkane such as methane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane; 4,4',3",4"-four Hydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',2",3",4"-pentahydroxy-3,5,3',5'-tetramethyl Hydroxytriphenylmethane such as triphenylmethane.

Further, examples of the acid chloride such as naphthoquinonediazide sulfonate chloride or benzoquinonediazide sulfonate chloride include 1,2-naphthoquinonediazide-5-. Sulfonyl chloride, 1, 2-naphthoquinonediazide-4-sulfonyl chloride, and the like.

In the radiation sensitive composition of the present embodiment, for example, each component is dissolved in a solvent as a homogeneous solution, and it is preferably prepared by filtering it with a filter having a pore size of about 0.2 μm, for example.

 [Characteristics of Radiation-Linear Compositions]  

Using the radiation sensitive composition of the present embodiment, an amorphous film can be formed by spin coating. Further, the radiation sensitive composition of the present embodiment can be applied to a general semiconductor manufacturing process. The type of the developing liquid to be used can be classified into any one of a positive resist pattern and a negative resist pattern.

In the case of the positive resist pattern, it is preferable that the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment has a dissolution rate of 5 Å/sec or less for the developing solution at 23 ° C, 0.05. It is better for ~5Å/sec, and it is better for 0.0005~5Å/sec. When the dissolution rate is 5 Å/sec or less, it is insoluble in the developing solution, and tends to be easily resisted. Moreover, when the dissolution rate is 0.0005 Å/sec or more, the resolution is improved. This is presumed to be a change in the solubility of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component before and after exposure, and is dissolved in the exposed portion of the developing solution and is not dissolved in the display. The contrast of the interface of the unexposed portion like the liquid becomes large. In addition, we also saw the reduction of LER and the effect of reducing it.

In the case of the negative resist pattern, it is preferable that the amorphous film formed by applying the radiation sensitive composition of the present embodiment has a dissolution rate of 10 Å/sec or more for the developing solution at 23 °C. When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is suitable for the resist. Moreover, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be caused by the dissolution of the micro surface portion of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component to reduce the LER. I also saw the effect of reducing the 瑕疵.

The dissolution rate is such that the amorphous film is immersed in a predetermined time developing solution at 23 ° C, and the film thickness before and after the immersion is determined by a known method such as a visual, ellipsometer or QCM method.

In the case of a positive resist pattern, the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser light, extreme ultraviolet light, electron beam or X-ray. Or, in the exposed portion after heating at 20 to 500 ° C, the dissolution rate of the developing solution at 23 ° C is preferably 10 Å / sec or more, and preferably 10 to 10000 Å / sec is preferably 100 to 1000 Å / sec. . When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is suitable for the resist. Moreover, when the dissolution rate is 10000 Å/sec or less, the resolution is also improved. This is presumed to be caused by the dissolution of the micro surface portion of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component to reduce the LER. I also saw the effect of reducing the 瑕疵.

In the case of the negative resist pattern, the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. Or, in the exposed portion after heating at 20 to 500 ° C, the dissolution rate of the developing solution at 23 ° C is preferably 5 Å / sec or less, preferably 0.05 to 5 Å / sec, preferably 0.0005 to 5 Å. /sec is better. When the dissolution rate is 5 Å/sec or less, the developing solution is insoluble, and it tends to be easily used as a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. It is presumed that the change in solubility before and after exposure of the resin containing the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component is dissolved in the unexposed portion of the developing solution and is not dissolved in The contrast of the interface of the exposure portion of the developing liquid is increased. In addition, we also saw the reduction of LER and the effect of reducing it.

 [mixing ratio of each component]  

In the radiation sensitive composition of the present embodiment, the content of the component (A) is any one of the total weight of the solid component (component (A), diazo naphthoquinone photoactive compound (B), and other components (D). The total solid content used is the same as 1 to 99% by mass, preferably 5 to 95% by mass, more preferably 10 to 90% by mass, particularly preferably 25 to 75% by mass. When the content of the component (A) in the radiation-sensitive composition of the present embodiment is within the above range, the pattern having a small roughness can be obtained with high sensitivity.

In the radiation sensitive composition of the present embodiment, the content of the diazo naphthoquinone photoactive compound (B) is the total weight of the solid component (component (A), diazo naphthoquinone photoactive compound (B), and other components. The total of the solid components used in any of (D) and the like, the same applies hereinafter, preferably 1 to 99% by mass, preferably 5 to 95% by mass, more preferably 10 to 90% by mass, particularly preferably 25 to 5% by mass. 75 mass%. When the content of the diazonaphthoquinone photoactive compound (B) of the radiation sensitive composition of the present embodiment is within the above range, there is a tendency that a pattern having a small roughness can be obtained with high sensitivity.

 [Other ingredients (D)]  

In the radiation sensitive composition of the present embodiment, an acid generator may be added as a component other than the component (A) and the diazo naphthoquinone photoactive compound (B), as long as the object of the present invention is not impaired. , cross-linking agent, acid diffusion control agent, dissolution promoter, dissolution control agent, sensitizer, surfactant, oxo acid or derivative of organic carboxylic acid or phosphorus, heat and/or photo-curing catalyst, polymerization Prohibition agent, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, pigment, tackifier, slip agent, antifoaming agent, coating agent, ultraviolet absorber, surfactant, One or two or more kinds of various additives such as a coloring agent and a nonionic surfactant. Further, in the present specification, the other component (D) is sometimes referred to as an arbitrary component (D).

In the radiation sensitive composition of the present embodiment, the blending ratio of each component (component (A) / diazonaphthoquinone photoactive compound (B) / optional component (D)) is based on the mass % of the solid content standard. 1~99/99~1/0~98 is preferred, preferably 5~95/95~5/0~49, more preferably 10~90/90~10/0~10, more preferably 20~ 80/80~20/0~5, especially good 25~75/75~25/0.

The mixing ratio of each component may be selected from various ranges in which the total synthesis can be made 100% by mass. When the blending ratio of each component of the radiation sensitive composition of the present embodiment is in the above range, in addition to the excellent roughness, the properties such as sensitivity and resolution tend to be excellent.

The radiation sensitive composition of the present embodiment may contain other resins in a range that does not inhibit the object of the present invention. Examples of such other resins include polymerization of a novolak resin, a polyvinyl phenol, a polyacrylic acid, a polyvinyl alcohol, a styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol or vinyl phenol as a monomer unit. Things or these derivatives. The amount of the resin to be added may be appropriately adjusted in accordance with the type of the component (A) to be used, and it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass per 100 parts by mass of the component (A). The amount is preferably 0 parts by mass or less.

 [Formation method of resist pattern]  

In the method for forming a resist pattern according to the present embodiment, the resist composition or the radiation sensitive composition of the present embodiment is used, and after forming a photoresist layer on the substrate, the resist layer is irradiated on a predetermined region of the photoresist layer. The step of radiation and imaging.

More specifically, the step of forming a resist film on the substrate by using the resist composition or the radiation sensitive composition of the present embodiment, the step of exposing the resist film, and developing the resist film to form an anti-etching film The steps of the etch pattern. The resist pattern in the present embodiment can also be formed as an upper layer resist in a multilayer process.

The method for forming the resist pattern is not particularly limited, and examples thereof include the following methods. First, a resist film or a radiation sensitive composition is applied onto a conventionally known substrate by a coating means such as spin coating, cast coating, or roll coating to form a resist film. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for an electronic component or a predetermined wiring pattern. More specifically, a metal substrate such as a germanium wafer, copper, chromium, iron, or aluminum, or a glass substrate can be given. Examples of the material of the wiring pattern include copper, aluminum, nickel, gold, and the like. Further, an inorganic or/or organic film may be provided on the substrate as necessary. An inorganic antireflection film (inorganic BARC) is mentioned as an inorganic film. An organic antireflection film (organic BARC) is mentioned as an organic film. The substrate may also be surface-treated by hexamethylenediazine or the like on the substrate.

Next, the substrate on which the resist composition or the radiation-sensitive composition is applied is heated as necessary. The heating condition varies depending on the composition of the resist composition or the radiation sensitive composition, and is preferably 20 to 250 ° C, preferably 20 to 150 ° C. It is preferable that the adhesion to the resist substrate is improved by heating. Next, the resist film is exposed to a desired pattern by any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. The exposure conditions and the like can be appropriately selected in accordance with the composition of the resist composition or the radiation-sensitive linear composition. In the present embodiment, since it is possible to stably form a high-precision fine pattern during exposure, it is preferable to perform heating after radiation irradiation. The heating condition may be changed by a composition of the resist composition or the radiation-sensitive linear composition, etc., preferably 20 to 250 ° C, preferably 20 to 150 ° C.

Next, a predetermined resist pattern is formed by developing the exposed resist film as a developing liquid. As the developing solution, a solubility parameter (SP value) close to the resin obtained by using the compound represented by the formula (1) or the formula (2) or the compound represented by the formula (1) or the formula (2) as a monomer is selected. The solvent is preferably used, and a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent or an ether solvent, a hydrocarbon solvent or an aqueous alkali solution can be used.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl group. Ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, ionone, diacetone alcohol, acetamethanol, phenylethyl Ketone, methylnaphthone, isophorone, propyl carbonate, and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. Diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl 3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, and the like.

Examples of the alcohol-based solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropanol (2-propanol), n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol. , isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-nonanol, etc., or ethylene glycol, diethylene glycol, three Glycol-based solvent such as ethylene glycol or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol A glycol ether solvent such as monoethyl ether or methoxymethylbutanol.

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

Examples of the guanamine-based solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and hexamethylphosphonium triamine. , 1,3-dimethyl-2-imidazolidinone, and the like.

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

The above solvent may be mixed in plural kinds, and a mixture with a solvent other than the above or water may be used within a range of properties. However, from the viewpoint of sufficiently achieving the effects of the present invention, the water content of the entire development liquid is preferably less than 70% by mass, preferably less than 50% by mass, and less than 30% by mass. It is more preferably, it is more preferably less than 10% by mass, and it is particularly preferable that it does not contain water substantially. In other words, the content of the organic solvent in the developing solution is preferably 30% by mass or more and 100% by mass or less based on the total amount of the developing liquid, and preferably 50% by mass or more and 100% by mass or less, and 70% or more. It is more preferably 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

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

In particular, the developing solution is selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether system from the viewpoint of improving the resist performance such as the resolution of the resist pattern or the roughness. A developing solution of at least one solvent of the solvent is preferred.

The vapor pressure of the developing solution is preferably 5 kPa or less at 20 ° C, preferably 3 kPa or less, and more preferably 2 kPa or less. When the vapor pressure of the developing liquid is 5 kPa or less, evaporation of the liquid on the substrate of the developing liquid or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved, and as a result, the dimensional uniformity in the wafer surface is good. The tendency to change.

Examples of the specific developing liquid having a vapor pressure of 5 kPa or less at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, and 2-hexyl a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methyl An ester solvent such as oxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate or propyl lactate; n- Propyl alcohol, isopropanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl An alcohol solvent such as an alcohol, n-octyl alcohol or n-nonanol; a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; ethylene glycol monomethyl ether or propylene glycol monomethyl ether; Ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxy a glycol ether solvent such as methyl butanol; an ether solvent such as tetrahydrofuran; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide A phthalamide solvent; an aromatic hydrocarbon solvent such as toluene or xylene; or an aliphatic hydrocarbon solvent such as octane or decane.

Examples of the specific developing liquid having a vapor pressure of 2 kPa or less at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, and 2-hexyl a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone or 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-ethoxy propionate, 3-methoxybutyl acetate , an ester solvent such as 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate or propyl lactate; n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol Alcohol solvent such as isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-nonanol; ethylene glycol, diethylene glycol Glycol solvent such as triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethyl Glycol ether solvent such as diol monoethyl ether or methoxymethylbutanol; N-methyl-2-pyrrolidone, N,N-dimethyl Aromatic hydrocarbon solvents Amides, N, N- acyl amine-based solvent is dimethylformamide, xylene and the like; octane, decane and other aliphatic hydrocarbon solvents.

In the developing solution, an appropriate amount of a surfactant may be added as necessary. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. For example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, and JP-A-62-170950 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The non-ionic surfactant is preferably the same as the surfactant described in the specification of No. 5,360,692, the specification of No. 5,529,881, the specification of No. 5,296,330, the specification of No. 5,546,098, the specification of No. 5,576,143, the specification of No. 5,294,411, and the specification of No. 5,842,451. . The nonionic surfactant is not particularly limited, and is preferably a fluorine-based surfactant or a lanthanoid surfactant.

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

As a developing method, for example, it can be applied to a method of immersing a substrate in a bath filled with a developing solution for a certain period of time (dipping method), and the developing liquid is allowed to stand on the surface of the substrate by surface tension and then left to stand for a certain period of time. In the method (stirring method), a method of spraying a developing solution on the surface of a substrate (spray method), and applying a developing solution to a nozzle at a constant speed at a constant speed while scanning, the coating liquid is continuously applied. Method (dynamic allocation method), etc. The time for performing the pattern development is not particularly limited, but is preferably 10 seconds to 90 seconds.

Further, after the step of developing the image, the step of stopping the development while replacing the solvent with another solvent can be carried out.

It is preferred to include a step of washing with a light lotion containing an organic solvent after development.

The light lotion used as the light-washing step after development is not limited to a resist pattern which is hardened by crosslinking, and is not particularly limited, and a solution or water generally containing an organic solvent can be used. . As the light washing liquid, a light lotion containing at least one type of organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is preferably used. After the development, it is preferred to carry out a step of washing with a light washing liquid containing at least one type of organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. More preferably, it is a step of washing with a light washing liquid containing an alcohol solvent or an ester solvent after development. More preferably, after the development, the step of washing with a light lotion containing a unit alcohol is carried out. It is particularly preferable to carry out a step of washing with a light washing liquid containing a unit alcohol having 5 or more carbon atoms after development. The time for performing the pattern light washing is not particularly limited, and is preferably from 10 seconds to 90 seconds.

Here, as the unit alcohol used in the light washing step after development, a linear, branched, or cyclic unit alcohol may be mentioned, and specifically, 1-butanol, 2-butanol, or 3-methyl- may be used. 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol , cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., and particularly preferred as a unit alcohol having 5 or more carbon atoms. 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

Each of the above components may be mixed in plural, and may be mixed with an organic solvent other than the above.

The water content in the light lotion is preferably 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less. When the water content in the light lotion is set to 10% by mass or less, there is a tendency that better development characteristics can be obtained.

The vapor pressure of the light washing liquid used for development is 0.05 kPa or more at 20 ° C, preferably 5 kPa or less, preferably 0.1 kPa or more and 5 kPa or less, and more preferably 0.12 kPa or more and 3 kPa or less. good. When the vapor pressure of the light lotion is 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface can be further improved, and the swelling due to the penetration of the light washing liquid can be further suppressed, and the size in the wafer surface is uniform. The tendency to be more benign.

An appropriate amount of surfactant can also be used in the light lotion.

In the light washing step, the wafer to be developed is subjected to a washing treatment using a light washing liquid containing the organic solvent. The method of the washing treatment is not particularly limited. For example, a method of continuously applying a light washing liquid on a substrate rotating at a constant speed (rotary coating method) can be applied, and the substrate is immersed in a tank filled with a light washing liquid for a certain period of time. a method (dipping method), a method of spraying a light washing liquid on a surface of a substrate (spraying method), etc., wherein the substrate is also subjected to a washing treatment by a spin coating method, and after the washing, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm. It is preferred to remove the light lotion from the substrate.

After the resist pattern is formed, the pattern wiring substrate can be obtained by etching. The etching method can be carried out by a known method such as dry etching using a plasma gas, wet etching such as an alkali solution, a second copper chloride solution, or a second iron chloride solution.

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

The residual resist pattern after etching can be peeled off by an organic solvent. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). Examples of the peeling method include a dipping method, a spraying method, and the like. Further, the wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate or may have a small-diameter through hole.

In the wiring substrate of the present embodiment, the metal can be vapor-deposited in a vacuum after forming a resist pattern, and then the resist pattern can be dissolved in a solution, which can be formed by lift-off.

 [Film forming composition for lithography used for underlayer film]  

The film forming composition for lithography (hereinafter also referred to as "lower film forming material") used in the underlayer film in the present embodiment contains a compound selected from the above formula (0) and the above formula (0) The resin obtained as a monomer is more specifically a compound represented by the above formula (1), a resin obtained by using the compound represented by the above formula (1) as a monomer, a compound represented by the formula (2), and a formula (2) At least one of a group of the obtained compounds as a monomer. The above-mentioned substance in the present embodiment is preferably from 1 to 100% by mass, and preferably from 10 to 100% by mass, based on the coating property and the quality stability. 50 to 100% by mass is better, and 100% by mass is particularly good.

The underlayer film forming material of the present embodiment may be used in a wet process and has excellent heat resistance and etching resistance. In addition, in the layer film forming material of the present embodiment, deterioration of the film at the time of high-temperature grilling is suppressed by using the above-mentioned substance, and an underlayer film excellent in etching resistance such as oxygen plasma etching can be formed. Further, since the film forming material of the present embodiment has excellent adhesion to the resist layer, an excellent resist pattern can be obtained. In addition, the underlayer film forming material of the present embodiment may contain a known underlayer film forming material for lithography, etc., within a range that does not impair the effects of the present invention.

 [solvent]  

In the present embodiment, the underlayer film forming material may contain a solvent. As a solvent used for the underlayer film forming material, those which are at least soluble in the above-mentioned materials can be used.

Specific examples of the solvent are not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; propylene glycol monomethyl ether and propylene glycol monomethyl ether B; Solvents such as acid esters; esters of ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc. A solvent; an alcohol solvent such as methanol, ethanol, isopropanol or 1-ethoxy-2-propanol; or an aromatic hydrocarbon such as toluene, xylene or anisole. These solvents may be used alone or in combination of two or more.

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

The content of the solvent is not particularly limited, and from the viewpoint of solubility and film formation, it is preferably 100 to 10,000 parts by mass, and 200 to 5,000 parts by mass, based on 100 parts by mass of the total mass of the solid component. Good, preferably 200 to 1,000 parts by mass.

 [crosslinking agent]  

In the present embodiment, the underlayer film forming material may contain a crosslinking agent as necessary from the viewpoint of suppressing mutual mixing and the like. The crosslinking agent is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

Specific examples of the crosslinking agent which can be used in the present embodiment include a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, an acrylate compound, a melamine compound, and a hydrazine. The amine compound, the ethylene glycol urea compound, the urea compound, the isocyanate compound, the azide compound, and the like are not particularly limited thereto. These crosslinking agents may be used alone or in combination of two or more. Among them, a benzoxazine compound, an epoxy compound or a cyanate compound is preferred, and a benzoxazine compound is preferred from the viewpoint of improving etching resistance.

As the phenol compound, a known one can be used. Examples of the phenols include, in addition to phenol, alkylphenols such as cresols and xylenols, polyvalent phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalenediols, and A bisphenol such as phenol A or bisphenol F, or a polyfunctional phenol compound such as a phenol novolak or a phenol aralkyl resin. Among them, an aralkyl type phenol resin is preferred from the viewpoint of heat resistance and solubility.

As the epoxy compound, a known one can be used, and it is selected from those having two or more epoxy groups in one molecule. Examples thereof include bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-bisphenol F, bisphenol S, bisphenol, 2,2'-bisphenol, 3,3' , 5,5'-tetramethyl-4,4'-dihydroxybisphenol, resorcinol, naphthalenediol, etc., epoxides of divalent phenols, ginseng-(4-hydroxyphenyl)methane, 1,1,2,2-indole (4-hydroxyphenyl)ethane, ginseng (2,3-epoxypropyl)isocyanurate, trishydroxymethylmethane triglycidyl ether, trishydroxyl Ethylene oxides, dicyclopentadienes and phenols of trivalent or higher phenols such as propane triglycidyl ether, trishydroxyethyl ethane triglycidyl ether, phenol novolac, o-cresol novolac An epoxide of a co-condensation resin, an epoxide of a phenol aralkyl resin synthesized from a phenol and a p-xylene dichloride, or the like, and a phenol and a bischloromethylbiphenyl group. An epoxide of a biphenyl aralkyl type phenol resin, an epoxide of a naphthol aralkyl resin synthesized from a naphthol and a p-xylene dichloride, or the like. These epoxy resins may be used alone or in combination of two or more. Among them, from the viewpoint of heat resistance and solubility, an epoxy resin obtained from a phenol aralkyl resin or a biphenyl aralkyl resin is preferably a solid epoxy resin at normal temperature.

The cyanate ester compound is not particularly limited as long as it has a compound having two or more cyanate groups in one molecule, and a known one can also be used. In the present embodiment, a preferred cyanate ester compound is 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 ester compound is preferably one having an aromatic group and a structure in which a cyanate group is directly bonded to an aromatic group. Examples of such a cyanate ester compound include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolak resin, and dicyclopentadiene novolac resin. , tetramethyl bisphenol F, bisphenol A novolak resin, brominated bisphenol A, brominated phenol novolac resin, trifunctional phenol, tetrafunctional phenol, naphthalene phenol, biphenyl phenol, phenol aralkyl A resin, a biphenyl aralkyl resin, a naphthol aralkyl resin, a dicyclopentadiene aralkyl resin, an alicyclic phenol, a phosphorus-containing phenol, or the like, which has a hydroxyl group substituted by a cyanate group. These cyanate ester compounds can be used singly or in combination of two or more kinds as appropriate. Further, the cyanate compound may be in any form of a monomer, an oligomer, and a resin.

As the above amine compound, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4, are exemplified. 4'-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3,4'-Diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl Base sulfide, 3,3'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-double (4-Aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, Bis[4-(3-aminophenoxy)phenyl]ether, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(4-amino-3-chlorophenyl) Ruthenium, 9,9-bis(4-amino-3-fluorophenyl)anthracene, O-triazine, m-triazine, 4,4'-diaminobenzimidazole Amine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4-aminophenyl-4-aminobenzoate, 2-(4-amino group Phenyl)-6-aminobenzoxazole and the like. Also, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-di Aminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 1,4- Bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-double ( 3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3- Aromatic phenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, aromatic amine such as bis[4-(3-aminophenoxy)phenyl]ether , diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, two Aminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[ 5.2.1.02,6]decane, 1,3-diaminomethylcyclohexane, isophor An aliphatic such as an alicyclic amine such as a diamine, an ethylenediamine, a hexamethylenediamine, an octamethylamine, a decylmethyldiamine, a diethylidenetriamine or a trisoleethyltetramine Amines, etc.

Examples of the benzoxazine compound include a Pd-type benzoxazine obtained from a difunctional diamine and a monofunctional phenol, and a Fa-type benzene derived from a monofunctional diamine and a difunctional phenol. And oxazine and so on.

Specific examples of the melamine compound include, for example, hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, a methoxymethylated compound of 1 to 6 methylol groups, or a mixture thereof. And hexamethoxyethyl melamine, hexamethoxymethyl melamine, hydroxymethyl group of hexamethylol melamine, 1 to 6 methoxymethylated compounds or a mixture thereof.

Specific examples of the guanamine compound include methoxymethylation of 1 to 4 methylol groups of tetramethylol decylamine, tetramethoxymethyl decylamine, and tetrahydroxymethyl decylamine. The compound or a mixture thereof, tetramethoxyethyl decylamine, tetradecyl decylamine, tetrahydroxymethyl decylamine, a 1,4-hydroxymethylmethylated compound or a mixture thereof, or the like.

Specific examples of the ethylene glycol urea compound include tetramethylol glycol urea, tetramethoxyethylene glycol urea, tetramethoxymethyl glycol urea, and tetrahydroxymethyl ethylene glycol. 1 to 4 methoxymethylated compounds of a hydroxymethyl group of a glycol urea or a mixture thereof, 1 to 4 methoxymethylated compounds of a hydroxymethyl group of tetramethylol glycol urea Or a mixture thereof, and the like.

Specific examples of the urea compound include, for example, a methoxymethylated compound of 1,4-hydroxymethyl urea, tetramethoxymethyl urea, and tetramethylol urea of 1 to 4 methylol groups or Mixture, tetramethoxyethyl urea, and the like.

Further, in the present embodiment, a crosslinking agent having at least one allyl group may be used from the viewpoint of crosslinkability. 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)anthracene, bis(3-allyl-4- Allyl phenol such as hydroxyphenyl) sulfide, bis(3-allyl-4-hydroxyphenyl)ether, 2,2-bis(3-allyl-4-c-phenylphenyl)propane 1,1,1,3,3,3-hexafluoro-2,2-bis(3-allyl-4-c-phenylphenyl)propane, bis(3-allyl-4-cyanate benzene Allyl cyanate, diene (3-allyl-4-c-phenylphenyl) sulfide, bis(3-allyl-4-c-phenylphenyl) ether, etc. Propyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diene The propyl ether, pentaerythritol allyl ether, and the like are not limited to these examples. These may be used alone or in a mixture of two or more types. These are also 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)fluorene, bis(3-allyl-4-hydroxyphenyl) sulfide, bis(3-allyl) Allyl phenols such as 4-hydroxyphenyl)ether are preferred.

The content of the crosslinking agent in the underlayer film forming material is not particularly limited, and is preferably from 0.1 to 50% by mass based on the total mass of the solid component, preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. . When the content of the crosslinking agent is set to the above range, the occurrence of a phenomenon of mixing with the resist layer tends to be suppressed, and the effect of preventing reflection is enhanced, and the film formability after crosslinking tends to be improved.

 [Crosslinking accelerator]  

In the layer film forming material of the present embodiment, a crosslinking accelerator which promotes crosslinking and curing reaction can be used as necessary.

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

The crosslinking accelerator is not limited to the following, and examples thereof include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, and benzyldimethyl Tertiary amines such as cisamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methyl Imidazoles such as imidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5-triphenylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine , organic phosphines such as diphenylphosphine and phenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium, ethyltriphenylborate, tetrabutylphosphonium, tetrabutylborate, etc. Instead of a tetraphenylboron salt such as tetrahedral borate, 2-ethyl-4-methylimidazolium tetraphenylborate or N-methylmorpholine or tetraphenylborate.

The content of the crosslinking accelerator is preferably 0.1 to 10% by mass based on the total mass of the solid component, and is preferably 0.1 to 5% by mass, more preferably 0.1 to 1 from the viewpoint of easy control and economy. 3 mass%

 [Free radical polymerization initiator]  

In the underlayer film forming material of the present embodiment, a radical polymerization initiator may be added as necessary. As the radical polymerization initiator, a photopolymerization initiator which can initiate radical polymerization by light or a thermal polymerization initiator which starts radical polymerization by heat can also be used. The radical polymerization initiator is, for example, at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peracid polymerization initiator, and an azo polymerization initiator.

The radical polymerization initiator is not particularly limited, and may be suitably used in the past. Examples thereof include 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyl). Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionate) -Phenylmethyl]phenyl}-2-methylpropan-1-one, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6- Ketone photopolymerization initiators such as trimethylbenzhydryl)-phenylphosphine oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl ethyl Indole acetate peroxide, acetamidine acetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-double (t -hexylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy) -2-methylcyclohexane, 1,1-bis(t-butylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-double (t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, p-calendane hydrogen peroxide, diisopropylbenzene peroxidation Hydrogen, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide T-hexyl hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, diisopropylbenzene peroxide, 2,5-dimethyl -2,5-bis(t-butylperoxy)hexane, t-butyl cumene peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5- Bis(t-butylperoxy)hexyne-3, isobutylguanidino peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, lauryl peroxide, stearic acid Mercapto peroxide, succinic acid peroxide, m-tolylbenzyl peroxide, benzhydryl peroxide, di-n-propyl peroxydicarbonate, diisopropyl Oxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate , bis-3-methoxybutylperoxydicarbonate, di-s-butylperoxydicarbonate, bis(3-methyl-3-methoxybutyl)peroxydicarbonate, α , α'-bis(new fluorenylperoxy)diisopropylbenzene, cumene peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1 -cyclohexyl-1-methylethyl peroxy neodecanoate , t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3 -tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexanoate, 1-cyclohexyl- 1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexyl Oxypropyl isopropyl carbonate, t-butyl peroxy isobutyrate, t-butyl peroxy malate, t-butyl peroxy-3,5,5-trimethylol (metol) hexanoic acid Ester, t-butylperoxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate , t-butyl peroxy-m-tolylmethyl benzoate, t-butyl peroxybenzoate, bis(t-butyl peroxy) isophthalate, 2,5- Dimethyl-2,5-bis(m-tolylmethyl peroxy)hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzylidene) Peroxy)hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsulfonyl peroxide, 3,3',4,4'-tetra(t-butylperoxy) Carbonyl An organic peroxide-based polymerization initiator such as benzophenone or 2,3-dimethyl-2,3-diphenylbutane.

Further, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and 1-[(1-cyano-1-methylethyl)azo]carbamamine are mentioned. 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2 , 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionate) dihydrochloride, 2,2'-azobis ( 2-methyl-N-phenylpropionate hydrazine) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionate]dihydride chloride , 2,2'-azobis[N-(4-hydrophenyl)-2-methylpropionate]dihydrochloride, 2,2'-azobis[2-methyl-N-( Phenylmethyl)phosphonium propionate]dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propionate]dihydrochloride, 2,2'- Azobis[N-(2-hydroxyethyl)-2-methylpropionate]dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2 -yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-( 4,5,6,7-tetrahydro-1H-1,3-dioxan-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3,4,5 ,6-tetrahydropyrimidin-2-yl)propane] Hydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azo Bis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2- Propyl], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide], 2,2'-even Nitrogen bis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propanamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl) Acetylamine], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2 '-Azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid) An azo polymerization initiator such as 2,2'-azobis[2-(hydroxymethyl)propanenitrile]. As the radical polymerization initiator in the present embodiment, one type of these may be used alone or two or more types may be used in combination, and other known polymerization initiators may be used in combination.

The content of the radical polymerization initiator is preferably a stoichiometric amount, preferably from 0.05 to 25% by mass based on the total mass of the solid component, and preferably from 0.1 to 10% by mass. When the content of the radical polymerization initiator is 0.05% by mass or more, the curing fraction may be prevented from being sufficient. On the other hand, when the content of the radical polymerization initiator is 25% by mass or less, it is possible to prevent The tendency of the underlayer film forming material to have long-term preservation stability at room temperature.

 [acid generator]  

In the present embodiment, the underlayer film forming material may contain an acid generator as necessary, from the viewpoint of further promoting the crosslinking reaction by heat. As the acid generator, those which generate an acid by thermal decomposition, generate an acid by light irradiation, or the like 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 underlayer film forming material is not particularly limited, and is preferably from 0.1 to 50% by mass based on the total mass of the solid component, and preferably from 0.5 to 40% by mass. When the content of the acid generator is set to the above range, the amount of acid generated is increased to increase the crosslinking reaction, and the occurrence of a phenomenon of mixing with the resist layer tends to be suppressed.

 [alkaline compound]  

In the present embodiment, the underlayer film forming material may contain a basic compound from the viewpoint of improving storage stability and the like.

The basic compound is a role as a quencher for an acid which is intended to prevent a trace amount of acid generated from an acid generator from undergoing a crosslinking reaction. The 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 underlayer film forming material is not particularly limited, and is preferably 0.001 to 2% by mass based on the total mass of the solid component, and is preferably 0.01 to 1% by mass. When the content of the basic compound is set to the above range, there is a tendency that the crosslinking stability is improved without excessive loss of the crosslinking reaction.

 [Other additives]  

Further, in the present embodiment, the underlayer film forming material may contain other resins and/or compounds for the purpose of controlling the imparting or absorbance by heat or light. Examples of such other resins and/or compounds include naphthol resins, xylene resin naphthol denatured resins, and phenol-modified resins of naphthalene resins; polyhydroxystyrene, dicyclopentadiene resins, and (meth)acrylates; a naphthalene ring such as dimethacrylate, trimethacrylate, tetramethacrylate, vinyl naphthalene or polydecene, biphenyl ring such as phenanthrenequinone or anthracene, thiophene or anthracene containing a heterocyclic ring having a hetero atom a resin or a resin not containing an aromatic ring; a rosin-based resin, a cyclodextrin, an adamantane (poly) alcohol, a tricyclodecane (poly)ol, and a resin or a compound containing an alicyclic structure, etc., but It is not particularly limited to this. Further, in the present embodiment, the underlayer film forming material may contain a known additive. The known additive is not limited to the following, and examples thereof include heat and/or photo-curing catalyst, polymerization inhibitor, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, and pigment. , tackifiers, slip agents, defoamers, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc.

 [Formation method of underlayer film for lithography and multilayer resist pattern]  

The underlayer film for lithography in the present embodiment is formed of the underlayer film forming material.

Further, in the resist pattern forming method of the present embodiment, the underlayer film is formed on the substrate by using the composition, and at least one photoresist layer is formed on the underlayer film, and then radiation is irradiated on a predetermined region of the photoresist layer. The steps of visualization. More specifically, the step (A-1) of forming the underlayer film using the underlayer film forming material of the present embodiment on the substrate, and the step (A-2) of forming at least one photoresist layer on the underlayer film are as described above. After the step A-2), the radiation is irradiated to a predetermined region of the photoresist layer to perform a development step (A-3).

Further, in the circuit pattern forming method of the present embodiment, the underlayer film is formed on the substrate by using the composition, and the interlayer film is formed on the underlayer film using a resist interlayer film material, and at least one layer is formed on the interlayer film. a step of forming a photoresist layer, irradiating radiation in a predetermined region of the photoresist layer, forming a resist pattern by developing, etching the intermediate layer film by using the resist pattern as a mask, and obtaining the intermediate layer film The step of etching the underlayer film as an etch mask and using the obtained underlayer film pattern as an etch mask to form a pattern on the substrate by etching the substrate.

More specifically, the step (B-1) of forming a lower layer film using the underlayer film forming material of the present embodiment on the substrate, and the use of a resist interlayer film material containing germanium atoms on the underlayer film to form an interlayer film are provided. Step (B-2), a step (B-3) of forming at least one photoresist layer on the intermediate layer film, and irradiating radiation in a predetermined region of the photoresist layer after the step (B-3), After the step (B-4) of forming a resist pattern and the step (B-4), the resist pattern is used as a mask to etch the interlayer film, and the obtained interlayer film pattern is used as an etching mask. The underlayer film is etched, and the obtained underlayer film pattern is used as an etching mask to etch the substrate, and then a step (B-5) is formed on the substrate.

The underlayer film for lithography in the present embodiment is not particularly limited as long as it is formed of the underlayer film forming material of the present embodiment, and a known method can be applied. For example, the underlayer film material of the present embodiment is applied to a substrate by a known coating method such as spin coating or screen printing, or a printing method, and then the organic solvent or the like is removed and removed, and then crosslinked and cured by a known method. The underlayer film for lithography of this embodiment is formed. Examples of the crosslinking method include heat curing and light curing.

In the formation of the underlayer film, it is preferable to apply a grilling while suppressing the occurrence of the mixed phenomenon with the upper resist and also promoting the crosslinking reaction. In this case, the grilling temperature is not particularly limited, and is preferably in the range of 80 to 450 ° C, preferably 200 to 400 ° C. Further, the grilling time is not particularly limited, and it is preferably in the range of 10 to 300 seconds. Further, the thickness of the underlayer film can be appropriately selected in accordance with the required properties, and is not particularly limited, and is usually preferably from 30 to 20,000 nm, preferably from 50 to 15,000 nm.

After the underlayer film is formed, in the two-layer process, a resist layer containing ruthenium or a single-layer resist formed of a general hydrocarbon can be formed thereon, and a ruthenium-containing intermediate layer is further formed on the top layer during the three-layer process, and further It is preferred to produce a single-layer resist layer containing no antimony on the upper surface. At this time, as a photoresist used when forming the resist layer, a known one can be used.

After the underlayer film is formed on the substrate, in the case of the two-layer process, a resist layer containing ruthenium or a single-layer resist formed of a general hydrocarbon can be formed on the underlayer film. In the case of the three-layer process, an intermediate layer containing germanium was formed on the underlayer film, and a single-layer resist layer containing no germanium was further formed on the intermediate layer containing germanium. In such a case, the photoresist material used for forming the resist layer can be suitably selected from known ones, and is not particularly limited.

From the viewpoint of oxygen etching resistance, a resist material containing ruthenium for a two-layer process is a polymer containing a ruthenium atom such as a polysilsesquioxane derivative or a vinyl decane derivative, and further used as a base polymer. It is preferred to use a positive photoresist material containing an organic solvent, an acid generator, and, if necessary, a basic compound. Among them, as the polymer containing a ruthenium atom, a known polymer used for such a resist material can be used.

As the intermediate layer containing ruthenium for the three-layer process, it is preferred to use an intermediate layer of a polysesquioxane group. Since the intermediate layer has an effect as an antireflection film, there is a tendency that reflection can be effectively suppressed. For example, in the case of a 193 nm exposure process, when a substrate having a high degree of etching resistance is used as a substrate containing a large number of aromatic groups, the k value tends to be high and the substrate reflection tends to be high. However, by suppressing reflection in the intermediate layer, the substrate can be made. The reflection is below 0.5%. The intermediate layer having such an antireflection effect is not limited to the following. However, as the 193 nm exposure, a polybenzazole having a phenyl group or a light-absorbing group introduced with a ruthenium-iridium bond may be used to crosslink under acid or heat. Oxygen is preferred.

Further, an intermediate layer formed by a Chemical Vapour Deposition (CVD) method can also be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following. For example, an SiON film is known. Generally, when the intermediate layer is formed by a spin coating method by a CVD method or a wet process such as screen printing, it is an advantage of being simpler and more costly. Moreover, the upper layer resist in the 3-layer process may be either a positive type or a negative type, and the same as the single-layer resist which is generally used.

Further, in the present embodiment, the underlayer film can be used as a general antireflection film for single-layer resist or a substrate for suppressing pattern dumping. Since the underlayer film is excellent in etching resistance for use in substrate processing, it is also expected to function as a hard mask for substrate processing.

In the case where the resist layer is formed of the above-mentioned photoresist material, a wet process such as a spin coating method or a screen printing method can be preferably used as in the case of forming the underlayer film. Further, after the resist material is applied by a spin coating method or the like, it is usually pre-baked, but the prebaking is preferably carried out in the range of 10 to 300 seconds at 80 to 180 °C. Thereafter, exposure is carried out according to a conventional method, and a resist pattern can be obtained by performing post-exposure bake (PEB) and development. Further, the thickness of the resist film is not particularly limited, and is preferably 30 to 500 nm, more preferably 50 to 400 nm.

Further, the exposed light can be appropriately selected and used in combination with the photoresist material to be used. Generally, a high-energy line having a wavelength of 300 nm or less is specifically an excimer laser of 248 nm, 193 nm, and 157 nm, a soft X-ray of 3 to 20 nm, an electron beam, an X-ray, or the like.

The resist pattern formed by the above method is suppressed by the pattern dump caused by the underlayer film. Therefore, by using the underlayer film in the present embodiment, a finer pattern can be obtained, and the necessary exposure amount must be reduced in order to obtain the resist pattern.

Here, the obtained resist pattern is etched as a mask. As the etching of the underlayer film in the two-layer process, it is preferable to use gas etching. As the gas etching, etching using oxygen is preferred. In addition to oxygen, an inert gas such as He or Ar or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ or H _{2 may be introduced} . Further, it is possible to perform gas etching using only CO, CO ₂ , NH ₃ , N ₂ , NO ₂ , and H ₂ gas without using oxygen. In particular, the latter gas may be used for sidewall protection to prevent Bottom Off of the sidewalls of the pattern.

On the other hand, for etching of the intermediate layer in the 3-layer process, it is preferred to use gas etching. As the gas etching, the same as those described in the above two-layer process can be applied. In other words, it is preferable to process the intermediate layer in the three-layer process to use a Freon-based gas to make the resist pattern mask. Thereafter, the intermediate layer pattern is masked as described above, for example, by oxygen etching, and the underlayer film can be processed.

When the inorganic hard mask intermediate layer film is formed as the intermediate layer, a tantalum oxide film, a tantalum nitride film, or a tantalum oxide nitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method of forming the nitride film is not limited to the following. For example, the method described in JP-A-2002-334869 (Patent Document 6) and WO2004/066377 (Patent Document 7) can be used. A photoresist film can be directly formed on the upper surface of the interlayer film, but an organic anti-reflection film (BARC) is spin-coated on the upper surface of the interlayer film to form a photoresist film thereon.

As the intermediate layer, an intermediate layer of a polysilsesquioxane bottom can also be used. By having the effect of using the resist interlayer film as an antireflection film, there is a tendency that reflection can be effectively suppressed. The specific material of the intermediate layer of the poly-sesquiterpoxyalkylene group is not limited to the following, and those described in JP-A-2007-226170 (Patent Document 8) and JP-A-2007-226204 (Patent Document 9) can be used.

Further, the second substrate etching can be carried out according to a conventional method. For example, if the substrate is SiO ₂ or SiN, etching with a Freon-based gas as a main component, and if p-Si, Al or W, a chlorine-based or bromine-based system can be used. Gas is etched as the main body. When the substrate is etched with a Freon-based gas, the ruthenium-containing resist of the two-layer resist process and the ruthenium-containing intermediate layer of the three-layer process are simultaneously peeled off from the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the peeling of the resist layer containing ruthenium or the intermediate layer containing ruthenium is performed separately, and generally, after the substrate processing, dry etching by Freon-based gas is performed.

In the present embodiment, the underlayer film is characterized by excellent etching resistance of the substrate. Further, the substrate can be appropriately selected and used, and is not particularly limited, and examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. Further, the substrate may be a laminate having a film to be processed (substrate to be processed) on a substrate (support). Examples of such a film to be processed include various Low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and barrier films thereof. Usually, a material different from the substrate (support) is used. Further, the thickness of the substrate to be processed or the film to be processed is not particularly limited, and is usually preferably from 50 to 10,000 nm, preferably from 75 to 5,000 nm.

 [resist permanent film]  

Further, the resist permanent film obtained by using the above composition and having the above-described composition can be formed into a permanent film which can be stored as a final product after forming a resist pattern as necessary. As a specific example of the permanent film, in the connection of the semiconductor device, a film may be affixed in the connection of the solder resist, the package material, the underfill material, the circuit component, or the like, or the connection layer of the integrated circuit device and the circuit substrate, and the thin display. A transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer, and the like. In particular, the permanent film formed of the above composition has excellent heat resistance or moisture resistance, and therefore has a very excellent advantage of being less polluting by the sublimation component. In particular, the display material is a material having high sensitivity, high heat resistance, and moisture absorbing reliability, which is less deteriorated by severely contaminated image quality.

When the above composition is used for a resistive permanent film, it is dissolved in an organic compound by adding other additives such as other resins, surfactants, dyes, fillers, crosslinking agents, and dissolution promoters which are further necessary as necessary for the addition of the curing agent. The solvent can be used as a composition for a resist permanent film.

The composition for forming a film for lithography or the composition for a resist permanent film can be adjusted by adding the above-mentioned respective components and mixing them by using a stirrer or the like. In addition, 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 adjusted by dispersing or mixing using a dispersing device such as a dissolving device, a homogenizer, or three roll mixers.

 [Examples]  

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

 (carbon concentration and oxygen concentration)  

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

Device: CHN coater MT-6 (Yanako Analytical Industry Co., Ltd.)

 (molecular weight)  

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

Further, gel permeation chromatography (GPC) analysis was carried out under the following conditions to obtain a weight average molecular weight (Mw), a number average molecular weight (Mn), and a dispersity (Mw/Mn) in terms of polystyrene.

Device: Shodex GPC-101 (Showa Denko (share) system)

Column: KF-80M×3

Dissolved solution: THF 1mL/min

Temperature: 40 ° C

 (solubility)  

The compound was stirred and dissolved at 23 ° C to become propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethyl urea (TMU). The 10% by mass solution was evaluated after one week based on the following criteria.

Evaluation A: By visual confirmation, no precipitates in all solvents

Evaluation C: Confirmation of precipitates in all solvents by visual inspection

 [Structure of compound]  

The structure of the compound was measured by ¹ H-NMR measurement under the following conditions using an "Advance 600 II spectrometer" manufactured by Bruker.

Frequency: 400MHz

Solvent: d6-DMSO

Internal standard: TMS

Measuring temperature: 23 ° C

 <Synthesis Example 1> Synthesis of XBisN-1  

2,6-naphthalenediol (a reagent manufactured by Sigma-Aldrich Co., Ltd.) 3.20 g (20 mmol) and 4-biphenylcarboxyaldehyde (Mitsubishi Gas Chemistry) in a 100 ml container equipped with a stirrer, a cooling tube and a burette To the company, 1.82 g (10 mmol) was charged with 30 mL of methyl isobutyl ketone, and 5 mL of 95% sulfuric acid was added thereto, and the reaction liquid was stirred at 100 ° C for 6 hours to carry out a reaction. Next, the reaction liquid was concentrated, 50 g of pure water was added thereto, and the reaction product was precipitated, and after cooling to room temperature, it was filtered and separated. The obtained solid was filtered, dried, and then purified by column chromatography to give 3.05 g of the desired compound. The chemical structure having the following formula was confirmed by 400 MHz - ¹ H-NMR.

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

δ (ppm) 9.7 (2H, O-H), 7.2~8.5 (19H, Ph-H), 6.6 (1H, C-H)

Further, the substitution position of 2,6-naphthalenediol was confirmed to be the first position by the proton signal of the third and fourth positions.

 <Synthesis Example 2> Synthesis of BisF-1  

Prepare a 200 mL inner container equipped with a stirrer, a cooling tube, and a burette. Into this container, 30 g (161 mmol) of 4,4-bisphenol (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 15 g (82 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 100 mL of butyl acetate were placed and added. P-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) 3.9 g (21 mmol), and a reaction liquid was prepared. The reaction solution was stirred at 90 ° C for 3 hours to carry out a reaction. After that, the reaction liquid was concentrated, and 50 g of heptane was added to precipitate a reaction product, which was cooled to room temperature, and then filtered and separated. The solid obtained by filtration was dried, and then separated and purified by column chromatography to obtain 5.8 g of the objective compound (BisF-1).

Further, the following absorption peak was found by 400 MHz - ¹ H-NMR, and it was confirmed to have a chemical structure of the following formula.

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

δ (ppm) 9.4 (4H, O-H), 6.8~7.8 (22H, Ph-H), 6.2 (1H, C-H)

The molecular weight of the obtained compound was determined by the above method to be 536.

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

Into a 100 mL inner container equipped with a stirrer, a cooling tube, and a burette, a liquid containing 9.8 g (21 mmol) of the compound represented by the above formula (XBisN-1) and 6.2 g (45 mmol) of potassium carbonate in 100 mL of acetone was placed. Further, bromoallyl 5.4 (45 mmol) g and 10-crown-6 2.0 g were added, and the resulting reaction solution was stirred under reflux for 7 hours to carry out a reaction. Thereafter, the solid component was removed by filtration through a reaction liquid, and after cooling in an ice bath, the reaction liquid was concentrated and solid matter was precipitated. The precipitated solid was filtered and dried, and then separated and purified by column chromatography to obtain 4.0 g of the objective compound of the formula (Al-XBisN-1).

The chemical structure of the following formula (Al-XBisN-1) was confirmed by 400 MHz - ¹ H-NMR.

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 determined by the above method to be 546.

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

The compound represented by the above formula (XBisN-1) was reacted in the same manner as in Synthesis Example 1 except for the compound represented by the above formula (BisF-1) to obtain the objective compound represented by the following formula (Al-BisF-1). 3.0g.

The chemical structure having the following formula (Al-BisF-1) was confirmed by 400 MHz - ¹ H-NMR.

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

δ (ppm) 6.8 to 7.8 (22H, Ph-H), 6.2 (1H, CH), 6.1 (4H, -CH=CH ₂ ), 5.4 to 5.5 (8H, -CH=CH ₂ ), for the obtained compound The result of measuring the molecular weight by the above method was 872.

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

6.1 g (11 mmol) of the compound of the above formula (Al-XBisN-1) was added to a vessel having a volume of 100 mL of a stirrer, a cooling tube and a burette, and 6.0 mL of the compound represented by the above formula (Al-XBisN-1) was stirred at 130 ° C for 6 hours. The reaction was carried out at 160 ° C for 24 hours. Next, 30 mL of water was added to the reaction liquid to precipitate crystals, which were separated by filtration. The obtained solid was filtered and dried, and then separated and purified by column chromatography to give the object compound of the formula:

The chemical structure of the following formula was confirmed by 400 MHz - ¹ H-NMR.

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

δ (ppm) 9.6 (2H, OH), 7.3 to 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 determined by the above method to be 546.

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

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

To a container having a volume of 100 mL containing a stirrer, a cooling tube, and a burette, 6.0 mL of a compound of the above formula (Al-BisF-1): 6.1 g (9 mmol) was added, and the reaction liquid was stirred at 130 ° C for 6 hours, and thereafter, The temperature was raised to 160 ° C and the reaction was carried out for 24 hours. Further, 30 mL of water was added to the reaction mixture to precipitate crystals, followed by filtration and separation. The obtained solid was filtered, dried, and then purified by column chromatography to obtain 1.05 g of the desired compound.

The chemical structure having the following formula was confirmed by 400 MHz - ¹ H-NMR.

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

δ (ppm) 9.4 (4H, OH), 6.8 to 7.8 (18H, Ph-H), 6.2 (1H, CH), 5.9 (4H, -CH=CH ₂ ), 4.9 (8H, -CH=CH ₂ ) 3.8(8H,-CH ₂ -)

The molecular weight of the obtained compound was determined by the above method to be 696.

The thermal decomposition temperature was 390 ° C, and the glass transition temperature was 200 ° C, which was confirmed to have high heat resistance.

 (Synthesis Example 3~10)  

Each of the target materials was obtained in the same manner as in Synthesis Example 1 except that 2,6-naphthalenediol and 4-biphenylcarboxyaldehyde of the starting material of Synthesis Example 1 were changed to the raw material 1 and the raw material 2 of Table 1.

Each was identified by 1H-NMR (Table 2).

 (Synthesis Examples 11 to 13)  

The raw material 2,6-naphthalenediol and 4-biphenylcarboxyaldehyde of the synthesis example 1 were changed to the raw material 1 and the raw material 2 of Table 3, and 1.5 mL of water and 73 mg (0.35 mmol) of dodecyl mercaptan were added. The reaction temperature was changed to 55 ° C, and the reaction temperature was changed to 55 ° C, and the same procedure as in Synthesis Example 1 was carried out to obtain each object.

Each was identified by 1H-NMR.

 (Synthesis Examples 3-1 to 13-1)  

The compound of the above formula (XBisN-1) of the starting material of Synthesis Example 1-1 was changed to the starting material 1 of Table 5, and the synthesis was carried out under the same conditions as in Synthesis Example 1-1 to obtain the objective compound. 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 Example 3-2 to 13-2)  

The compound of the above formula (Al-XBisN-1) of the starting material of Synthesis Example 1-2 was changed to the starting material 1 of Table 5, and the synthesis was carried out under the same conditions as in Synthesis Example 1-2 to obtain each object. . 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 Example 14) Synthesis of Resin (R1-XBisN-1)  

A four-necked flask containing an internal volume of 1 D with a Dimro reflux cooling tube, a thermometer and a stirring blade was prepared. Into the four-necked flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 21.0 g of a 40% by mass aqueous formaldehyde solution (manufactured as 280 mmol of formaldehyde, Mitsubishi Gas) were added to the compound (XBisN-1) obtained in Synthesis Example 1 in a nitrogen gas stream. Chemical (manufactured by the company) and 0.97 mL of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were reacted under reflux at 100 ° C for 7 hours under normal pressure. Thereafter, 180.0 g of o-xylene (Special grade of Wako Pure Chemical Industries, Ltd.) was added to the reaction liquid as a diluent solvent, and after standing, the aqueous phase of the lower phase was removed. Further, neutralization and water washing were carried out, and o-xylene was distilled off under reduced pressure to give 34.1 g of a brown solid resin (R1-XBisN-1).

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

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

A four-necked flask containing an internal volume of 1 D with a Dimro reflux cooling tube, a thermometer and a stirring blade was prepared. Into the four-necked flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 4-diphenylaldehyde 50.9 g (280 mmol, Mitsubishi Gas Chemicals) of the compound (XBisN-1) obtained in Synthesis Example 1 was placed in a nitrogen gas stream. 100 mL of anisole (manufactured by Kanto Chemical Co., Ltd.) and 10 mL of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) were reacted under reflux at 100 ° C for 7 hours under normal pressure. Thereafter, 180.0 g of o-xylene (Special grade of Pharmacopoeia manufactured by Wako Pure Chemical Industries, Ltd.) was added as a diluent solvent to the reaction liquid, and after standing, the aqueous phase of the lower phase was removed. Further, the mixture was neutralized and washed with water, and the solvent of the organic phase and the unreacted 4-biphenylaldehyde were distilled off under reduced pressure to give a brown solid resin (R2-XBisN-1) 34.7 g.

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

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

30 g of the above resin (R1-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were placed in 100 ml of dimethylformamide and acetic acid-2 was added to a vessel having a volume of 500 ml of a stirrer, a cooling tube and a burette. 13.12 g (108 mmol) of chloroethyl ester, and the reaction liquid was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath, and crystals were precipitated, filtered, and separated. 40 g of the above-mentioned crystals, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having an inner volume of 100 ml of a stirrer, a cooling tube, and a burette, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Thereafter, it was cooled in an ice bath, and the reaction liquid was concentrated, and the solid matter was precipitated and filtered, and dried to obtain a resin (Al-R1-XBisN-1) obtained as a brown solid resin (Al-R1-XBisN-1) 26.5 g. It is Mn: 2076, Mw: 3540, Mw/Mn:.

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

20.0 g of the resin of the above formula (R1-XBisN-1) and vinylbenzyl chloride (trade name CMS-P; Seimi Chemical) were placed in a 500 ml container equipped with a stirrer, a cooling tube and a burette. Preparation) 12.8g was added to 200ml of dimethylformamide, heated at 50 ° C and stirred, adding 26.0g of 28wt% sodium methoxide (methanol solution) by a titration funnel for 20 minutes, the reaction solution The reaction was carried out by stirring at 50 ° C for 1 hour. Next, 3.2 g of 28 wt% sodium methoxide (methanol solution) was added, and the reaction liquid was heated at 60 ° C and stirred for 5 hours, and then added with 8 g of 85 wt% citric acid, stirred for 10 minutes, and then cooled to 40 ° C to react. The liquid was dropped into pure water and the precipitated solid was filtered, and after drying, it was cooled to 50 ° C, and the reaction liquid was dropped into pure water and the precipitated solid was filtered, and dried to obtain a gray solid (AlOH- The resin represented by R1-XBisN-1) was 27.2 g.

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

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

30 g of the above resin (R2-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were placed in 100 ml of dimethylformamide in a vessel having a volume of 500 ml equipped with a stirrer, a cooling tube and a burette, and acetic acid-2- was added thereto. 13.12 g (108 mmol) of chloroethyl ester, and the reaction liquid was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath, and crystals were precipitated, filtered, and separated. 40 g of the above-mentioned crystals, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having an inner volume of 100 ml of a stirrer, a cooling tube, and a burette, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Thereafter, the mixture was cooled in an ice bath, and the reaction mixture was concentrated, and the solid matter was precipitated and filtered, and dried to give a brown solid solid (Al-R2-XBisN-1) (22.3 g).

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

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

In place of the above formula (Al-R1-XBisN-1) obtained in Synthesis Example 14-1, 40.5 g of the compound represented by the above formula (Al-R2-XBisN-1) obtained in Synthesis Example 15-1 was used. The reaction was carried out in the same manner as in Synthesis Example 14-2 to obtain 36.8 g of a resin of (AlOH-R2-XBisN-1) as a pale gray solid.

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

 <Synthesis Comparative Example 1>  

A four-necked flask of 10 L in internal volume with a Dymro reflux cooling tube, a thermometer and a stirring blade was prepared. In the four-necked flask, 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.1 kg of a 40% by mass aqueous formaldehyde solution were placed in a nitrogen gas stream (as formaldehyde 28 mol, Mitsubishi Gas Chemical ( (manufactured by the company) and 0.97 ml of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), and reacted under reflux at 100 ° C for 7 hours under normal pressure. Then, 1.8 kg of ethylbenzene (Special grade of the reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction liquid as a diluent solvent, and after standing, the aqueous phase of the lower phase was removed. After neutralizing and washing with water, ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to give 1.25 kg of dimethylnaphthalene formaldehyde resin as a pale brown solid.

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

Continue to prepare a four-necked flask with a volume of 0.5 L of the Dimro reflux cooling tube, thermometer and stirring wing. Into the four-necked flask, 100 g (0.51 mol) of dimethylnaphthalene formaldehyde resin and 0.05 g of p-toluenesulfonic acid obtained as described above were placed under a nitrogen stream, and the mixture was heated to 190 ° C for 2 hours, and then stirred. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the mixture was heated to 220 ° C and reacted for 2 hours. After the solvent was diluted, it was neutralized and washed with water, and the solvent was removed under reduced pressure to give 126.1 g of a dark brown solid densified resin (CR-1).

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

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

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

Further, each of the underlayer film forming materials for lithography having the composition shown in Table 6 was prepared. Then, these underlayer film forming materials for lithography were spin-coated on a ruthenium substrate, and then baked at 240 ° C for 60 seconds, and further baked at 400 ° C for 120 seconds to prepare an underlayer film each having a film thickness of 200 nm. The following are used for the acid generator, the crosslinking agent, and the organic solvent.

Acid generator: manufactured by Green Chemical Co., Ltd. Di-tert-butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI)

Crosslinking agent: NicaracMX270 (Nicarac) manufactured by Sanwa Chemical Co., Ltd.

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

‧Phenolic varnish: PSM4357 manufactured by Qunrong Chemical Co., Ltd.

Further, each of the underlayer film forming materials for lithography having the composition shown in Table 7 below was prepared. Then, these lithographic underlayer film forming materials were spin-coated on the ruthenium substrate, and after 60 seconds of baking at 110 ° C to remove the solvent of the coating film, the integrated exposure amount was 600 mj/cm ² and the irradiation time was 20 by a high pressure mercury lamp. The film was hardened in seconds, and a film having a film thickness of 200 nm was produced. The photoacid generator, the crosslinking agent, and the organic solvent are as follows.

‧Free radical polymerization initiator: IRGACURE 184 manufactured by BASF

‧ Crosslinking agent: Mitsubishi Gas Chemicals Diallyl bisphenol A type cyanate (DABPA-CN)

Xiaoxi Chemical Industry, diallyl bisphenol A (BPA-CA)

Xiaoxi Chemical Industry Benzoxazine (BF-BXZ)

Nippon Chemical Co., Ltd. Biphenyl aralkyl type epoxy resin (NC-3000-L)

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

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

(In the above formula, n is an integer from 1 to 4)

(NC-3000-L)

 [etching resistance]  

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

 [etching test]  

Etching device: RIE-10NR manufactured by Samco International

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

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

The evaluation of the etching resistance was carried out as follows.

A novolac underlayer film was produced under the same conditions as in Example 1 except that a novolac (PSM 4357 manufactured by Kyoei Chemical Co., Ltd.) was used as the substitution compound (AlOH-XBisN-1). The underlayer film of the novolac was subjected to the above etching test, and the etching rate at this time was measured.

Next, the lower layer films of Examples 1-1 to 2 and Comparative Example 1 were subjected to the same etching test as described above, and the etching rate at this time was measured. On the basis of the etching rate of the underlayer film of the novolak, the etching resistance was evaluated in accordance with the following evaluation criteria.

 [Evaluation Benchmark]  

A: The etching rate is less than -10% compared with the film under the novolac

B: The etching rate is -10% to +5% compared to the film under the novolac

C: The etching rate is more than +5% compared to the film under the novolac

 <Examples 38 to 39>  

Next, each solution of the underlayer film forming material for lithography containing AlOH-XBisN-1 or AlOH-BisF-1 obtained in Examples 1-1 and 2-1 was applied onto a SiO ₂ substrate having a thickness of 300 nm. After baking at 240 ° C for 60 seconds and then baking at 400 ° C for 120 seconds, a film having a film thickness of 70 nm was formed. A resist solution for ArF was applied onto the underlayer film, and a photoresist layer having a film thickness of 140 nm was formed by baking at 130 ° C for 60 seconds. Further, as the ArF resist solution, a compound to which the following formula (11) is added: 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass of the modulator.

The compound of the formula (11) is 4-methyl-2-methylpropenyl adamantane 4.15 g, methacryloxy-γ-butyrolactone 3.00 g, 3-hydroxy-1-adamantyl group 2.08 g of acrylate and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran as a reaction solution. The reaction solution was kept at 63 ° C under a nitrogen atmosphere, and after polymerization for 22 hours, the reaction solution was dropped into 400 ml of N-hexane. The resulting resin thus obtained was subjected to solidification purification, and the resulting white powder was filtered and dried under reduced pressure at 40 ° C overnight.

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

Next, an electron beam painting apparatus (ELS-7500, 50 keV) was used to expose the photoresist layer, and a 90 second barbecue (PEB) was performed at 115 ° C by using 2.38 mass % tetramethylammonium hydroxide ( The TMAH aqueous solution was subjected to 60 second development to obtain a positive resist pattern.

The shape and defect of the obtained resist pattern of 55 nmL/S (1:1) and 80nmL/S (1:1) were observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd.

For the shape of the resist pattern after development, if it is a non-pattern, the person with good rectangularity is evaluated as "good", and the others are evaluated as "poor". Further, the above observation results in the absence of a pattern, and the squareness is a good minimum line width as "resolution" as an evaluation index. Moreover, the minimum electron beam energy that can be drawn by a good figure shape is used as a "sensitivity" as an indicator of evaluation.

The evaluation results are shown in Table 8.

 <Comparative Example 2>  

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

As shown in Table 8, in the examples using the underlayer forming material of the compound of the present embodiment, the resist pattern shape after development was good, and no defects were observed. In comparison with Comparative Example 2 in which the formation of the underlayer film was omitted, it was confirmed that both the resolution and the sensitivity were remarkably excellent.

From the dissimilarity of the resist pattern shape after development, it is preferable that the underlayer film forming material for lithography used in Examples 38 to 39 exhibits adhesion to the resist material.

As shown in Table 1, in Examples 1-1 and 2-1 using AlOH-XBisN-1 or AlOH-BisF-1, at least heat resistance, solubility, and etching resistance were confirmed as compared with Comparative Example 1. One is good. On the other hand, in Comparative Example 1 using CR-1 (phenol-denatured dimethylnaphthalene formaldehyde resin), the etching resistance was poor.

Further, in Examples 38 to 39, the shape of the resist pattern after development was good, and it was confirmed that no defects were observed. Further, compared with Comparative Example 2 in which the formation of the underlayer film was omitted, it was confirmed that both the resolution and the sensitivity were remarkably excellent.

Further, from the viewpoint of the difference in the shape of the resist pattern after development, the underlayer film forming materials for lithography used in Examples 38 to 39 were also confirmed to have good adhesion to the resist material.

 <Examples 40 to 41>  

A solution of the underlayer film forming material for lithography of Examples 1-1 and 2-1 using AlOH-XBisN-1 or AlOH-BisF-1 was applied onto a SiO ₂ substrate having a thickness of 300 nm, and subjected to 240 ° C for 60 seconds. Then, after baking at 400 ° C for 120 seconds, a film having a film thickness of 80 nm was formed. An intermediate layer material containing ruthenium was applied onto the underlayer film, and after baking at 200 ° C for 60 seconds, an intermediate layer film having a film thickness of 35 nm was formed. Further, the above ArF resist solution was applied onto the interlayer film, and after baking at 130 ° C for 60 seconds, a photoresist layer having a film thickness of 150 nm was formed. Further, as the intermediate layer material containing ruthenium, a ruthenium atom-containing polymer obtained as follows was used.

In 200 g of tetrahydrofuran (THF) and 100 g of pure water, 16.6 g of 3-carboxypropyltrimethoxydecane, 7.9 g of phenyltrimethoxydecane and 14.4 g of 3-hydroxypropyltrimethoxydecane were dissolved, and the liquid temperature was set. 5 g of oxalic acid was added dropwise at 35 ° C, and then the temperature was raised to 80 ° C to carry out a condensation reaction of decyl alcohol. Next, 200 g of diethyl ether was added, and the aqueous layer was separated. The organic layer was washed twice with ultrapure water, and 200 g of propylene glycol monomethyl ether acetate (PGMEA) was added to heat the liquid to 60 ° C. The THF and diethyl ether water were removed by pressing to obtain a polymer containing a ruthenium atom.

Next, an electron beam painting apparatus (ELS-7500, 50 keV) was used to expose the photoresist layer, and a 90 second barbecue (PEB) was performed at 115 ° C by using 2.38 mass % tetramethylammonium hydroxide ( The TMAH) aqueous solution was subjected to 60 second development to obtain a positive resist pattern of 55 nmL/s (1:1).

Thereafter, RIE-10NR manufactured by Samco International Co., Ltd. was used, and the obtained resist pattern was used as a mask to perform dry etching of an interlayer film (SOG) containing ruthenium, and the obtained interlayer film pattern containing ruthenium was continuously used. The dry etching process of the underlying film of the mask and the dry etching process of the SiO ₂ film using the obtained underlying film pattern as a mask are sequentially performed.

Each etching condition is as follows.

Etching conditions for a resist pattern intermediate resist film

Output: 50W

Pressure: 20Pa

Time: 1min

Etching gas

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

Etching conditions of the resist underlayer film of the resist interlayer film pattern

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

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

Etching conditions of SiO ₂ film by resist underlayer pattern

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

Ar gas flow: C ₅ F ₁₂ gas flow: C ₂ F ₆ gas flow: O ₂ gas flow = 50: 4: 3: 1 (sccm)

 [assessment]  

The cross-section of the pattern (the shape of the SiO ₂ film after the etching) obtained as described above was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., and it was confirmed that the layer film was used in the multilayer film of the embodiment. The shape of the SiO ₂ film after etching in the etching process was a rectangle, and no defect was confirmed.

 [Examples 42 to 45]  

Using the respective compounds synthesized in the above Synthesis Examples, an optical component forming composition was blended as shown in Table 9 below. Further, among the components of the optical component forming composition in Table 9, the following were used for the acid generator, the crosslinking agent, the acid diffusion inhibitor, and the solvent.

‧Acid generator: Dibutyl butyl diphenyl iodonium nonafluoromethane sulfonate (DTDPI) manufactured by Green Chemical Co., Ltd.

Crosslinking agent: NicaracMX270 (Nicarac) manufactured by Sanwa Chemical Co., Ltd.

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

The composition of the optical component in a uniform state was spin-coated on a clean wafer, and then prebaked (prebake: PB) in an oven at 110 ° C to form an optical component forming film having a thickness of 1 μm. The composition for forming the optical component to be prepared was evaluated as "A" when the film was formed well, and was evaluated as "C" when the film formed was defective.

After the uniform optical component forming composition was spin-coated on the cleaned wafer, PB was performed in an oven at 110 ° C to form a film having a thickness of 1 μm. For this film, a refractive index (λ = 589.3 nm) at 25 ° C was measured using a multi-incidence angle spectroscopic ellipsometer VASE manufactured by JA Woollam. The film to be prepared was evaluated as "A" when the refractive index was 1.65 or more, "B" when it was 1.6 or more, and "C" when it was less than 1.6. Further, when the transmittance (λ = 632.8 nm) was 90% or more, it was evaluated as "A", and when it was less than 90%, it was evaluated as "C".

 [Examples 46 to 49]  

Using the respective compounds synthesized in the above Synthesis Examples and Examples, the resist compositions were blended as shown in Table 10 below. Further, among the components of the resist composition in Table 10, the following are used for the radical generator, the radical diffusion inhibitor, and the solvent.

‧Free radical polymerization initiator: IRGACURE 184 manufactured by BASF

‧Free radical diffusion control agent: IRGACURE1010 manufactured by BASF

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

 [evaluation method]    (1) Preservation stability and film formation of the resist composition  

The storage stability of the anticorrosive composition was set to a resist composition, and then allowed to stand at 23 ° C and 50% RH for 3 days, and the presence or absence of precipitation was visually observed. The resist composition after standing for 3 days was evaluated as A when it was a homogeneous solution without precipitation, and as C when it was precipitated. Further, after the resist composition in a uniform state was spin-coated on the cleaned wafer, the pre-exposure bake (PB) was performed in an oven at 110 ° C to form a resist film having a thickness of 40 nm. For the prepared resist composition, when the film was formed to be good, it was evaluated as A, and the formed film was evaluated as C.

 (2) Pattern evaluation of resist pattern  

After the uniform resist composition was spin-coated on the cleaned wafer, the pre-exposure bake (PB) was performed in an oven at 110 ° C to form a resist film having a thickness of 60 nm. For the obtained resist film, an electron beam drawing device (ELS-7500, manufactured by Ellionics Co., Ltd.) was used to irradiate a line of 1:1 line and space set at intervals of 50 nm, 40 nm, and 30 nm. After the irradiation, the resist film was heated at a predetermined temperature for 90 seconds, and immersed in PGME for 60 seconds for development. Thereafter, the resist film was washed in ultrapure water for 30 seconds and dried to form a negative resist pattern. With respect to the formed resist pattern, the line and the space were observed by a scanning electron microscope (S-4800 manufactured by Hitachi High Technology Co., Ltd.), and the reactivity was evaluated by electron beam irradiation of the resist composition.

Sensitivity indicates the minimum energy per unit area necessary to obtain a pattern, and is evaluated based on the following.

A: The case where the pattern is obtained at less than 50 μC/cm ²

C: A case where a pattern is obtained at 50 μC/cm ² or more

The pattern was formed by observing the obtained pattern shape by SEM (Scanning Electron Microscope) and evaluating it according to the following.

A: The case of getting a rectangular pattern

B: When you get an almost rectangular pattern

C: The case of obtaining a non-rectangular pattern

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

The compound and the resin of the present embodiment have high solubility in a safe solvent, and are excellent in heat resistance and etching resistance, and the resist composition of the present embodiment can impart a good resist pattern shape.

Further, it is possible to form a composition which can be applied to a wet process, and which is a useful compound for forming a photoresist underlayer film which is excellent in heat resistance and etching resistance, a resin, and a film for lithography. On the other hand, the film forming composition for lithography has a high heat resistance and a high solvent solubility, and has a compound or a resin having a specific structure. The deterioration of the film during high-temperature baking is suppressed, and etching resistance such as oxygen plasma etching can be formed. Excellent corrosion and underlayer film. Further, when the underlayer film is formed, the adhesion to the resist layer is also excellent, so that an excellent resist pattern can be formed.

Moreover, it is also useful as a composition for forming various optical components because of its high refractive index and suppression of coloration by low-temperature to high-temperature treatment.

Therefore, the present invention can be used for electrical insulating materials, resist resins, semiconductor sealing resins, adhesives for printed circuit boards, electrical equipment, electronic equipment, industrial equipment, and the like. Base resin, pre-preg base material, cumulative laminate material, fiber reinforced plastic resin, liquid crystal display panel sealing resin, paint, various coating agents, adhesives, semiconductor coating agents, semiconductors A plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast upward lens, etc.), which is used for a resist resin, a resin for forming an underlayer film, a film or a sheet, A phase difference film, a film for electromagnetic wave shielding, a prism, an optical fiber, a solder resist for a flexible printed wiring, an electroplating resist, an interlayer insulating film for a multilayer printed wiring board, and an optical component such as a photosensitive optical waveguide can be widely and effectively used. Use.

The present application is based on Japanese Patent Application No. Hei. No. Hei. No. Hei.

 [Industrial availability]  

The present invention has industrial applicability in the field of resist for lithography, underlayer film for lithography, multilayer underlayer film for resist, and optical parts.

Claims (28)

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 of R ^{T is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have The aryl group having 6 to 30 carbon atoms of the substituent, the alkenyl group having 2 to 30 carbon atoms which may have a substituent, the alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, wherein the alkyl group, the aryl group, the above alkenyl group and the alkoxy group may contain an ether bond, a keto bond or an ester bond, wherein at least one of R ^T is a hydroxyl group and R At least one of ^{T is} an alkenyl group having 2 to 30 carbon atoms, X represents an oxygen atom, a sulfur atom, a single bond or no crosslink, and m is independently an integer of 0 to 9, wherein at least one of m is 2 An integer of ~9 or at least two of m is an integer from 1 to 9, and N is an integer from 1 to 4. When N is an integer of 2 or more, the structural formulas in N [ ] may be the same or different. r is independently an integer from 0 to 2). The compound of claim 1, wherein the compound represented by the above formula (0) is a compound represented by the following formula (1); (In the formula (1), R ⁰ has the same meaning as the above R ^Y , R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms, and R ² to R ^{5 are} each independently a carbon number 1 to 30 which may have a substituent. The alkyl group, the aryl group having 6 to 30 carbon atoms which may have a substituent, the alkenyl group having 2 to 30 carbon atoms which may have a substituent, the alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the aforementioned alkoxy group may have an ether bond, a keto bond or an ester bond, wherein R ² to R ⁵ At least one of R ² to R ^{5 is} an alkenyl group having 2 to 30 carbon atoms, m ² and m ^{3 are} each independently an integer of 0 to 8, and m ⁴ and m ^{5 are} each independently 0. An integer of ~9, but m ² , m ³ , m ⁴ and m ^{5 are} not 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 integers of 1 to 8 or 1 to 9, and n is the same meaning as the above N, wherein n is an integer of 2 or more, and n structural formulas in [ ] They may be the same or different, and p ² to p ^{5 are} each independently the same as the aforementioned r). The compound of claim 1, wherein the compound represented by the above formula (0) is a compound represented by the following formula (2); (In the formula (2), R ^0A has the same meaning as the above R ^Y , R ^1A is a n ^A valent group or a single bond having 1 to 30 carbon atoms, and R ^{2A is} each independently a carbon number of 1 to 30 which may have a substituent. a 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 alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, and a nitro group And an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the aforementioned alkenyl group and the alkoxy group may contain an ether bond, a keto bond or an ester bond, wherein at least one of R ^2A is a hydroxyl group Further, at least one of R ^{2A is} an alkenyl group having 2 to 30 carbon atoms, and n ^A has the same meaning as the above-mentioned N. 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 no cross-linking, and m ^{2A is} independently an integer of 0-7, but at least one m ^2A is an integer of 2-7 or at least 2 m ^2A is 1 An integer of ~7, q ^{A is} independently 0 or 1). The compound of claim 2, wherein the compound represented by the above formula (1) is a compound represented by the following formula (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 have the} same meanings as defined above, and R ⁶ to R ⁷ each independently may have a substitution. An alkyl group having 1 to 30 carbon atoms, 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 amine group, and a carboxylic acid 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, and m ⁶ and m ^{7 are} each independently an integer of 0 to 7. However, m ⁴ , m ⁵ , m ⁶ and m ⁷ will not be 0) at the same time. The compound of claim 4, wherein the compound represented by the above formula (1-1) is a compound represented by the following formula (1-2); (In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ^{7 have the} same meanings as defined above, R ⁸ to R ⁹ In the same meaning as the above R ⁶ to R ⁷ , R ¹² to R ^{13 have the} same meaning as the above R ¹⁰ to R ¹¹ , and m ⁸ and m ^{9 are} each independently an integer of 0 to 8, but m ⁶ , m ⁷ , m ⁸ and m ⁹ will not be 0) at the same time. The compound of claim 3, wherein the compound represented by the above formula (2) is a compound represented by the following formula (2-1); (In the formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^{A have the} same meanings as defined above, and each of R ^{3A is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have a substitution. An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group, wherein at least one of R ^3A is The alkenyl group having 2 to 30 carbon atoms, each of R ^{4A is} independently a hydrogen atom, and m ^{6A is} independently an integer of 0 to 5).  A resin characterized by being a monomer of the compound of claim 1 as a monomer.   a resin according to claim 7, which has a structure represented by the following formula (3); (In the formula (3), L is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and an extended aryl group having 6 to 30 carbon atoms which may have a substituent. a stearoxy group or a single bond having 1 to 30 carbon atoms which may have a substituent, and the alkylene group, the above-mentioned extended aryl group and the aforementioned alkoxy group may have an ether bond, a keto bond or an ester bond, and R ⁰ and the aforementioned R ^{Y has the} same meaning, R ¹ is an n-valent or single bond having 1 to 60 carbon atoms, and R ² to R ^{5 are} each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and a carbon number 6 which may have a substituent. An aryl group of ~30, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group a hydroxyl group, the alkyl group, the aryl group, the above alkenyl group and the alkoxy group may have an ether bond, a keto bond or an ester bond, wherein at least one of R ² to R ⁵ is a hydroxyl group, and R ² to R ⁵ At least one of them is an alkenyl group having 2 to 30 carbon atoms, m ² and m ^{3 are} each independently an integer of 0 to 8, and m ⁴ and m ^{5 are} each independently an integer of 0 to 9, but m ² , m ³ , m ⁴ and m ^{5 are} not 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 or m ³ , At least two of m ⁴ and m ⁵ are 1 to 8 or an integer of 1 to 9). a resin according to claim 7, which has a structure represented by the following formula (4); (In the formula (4), L is a linear or branched alkyl or single bond having a carbon number of 1 to 30, R ^0A has the same meaning as the above R ^Y , and R ^1A is a carbon number of 1 to 30 n ^A a valence group or a single bond, each of R ^2A independently being an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 2 to 30 which may have a substituent An alkenyl group, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the above alkyl group, the above aryl group, the aforementioned 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, and n ^A has the same meaning as the aforementioned N. 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 no crosslink, and m ^{2A is} independently 0 to 7 An integer, but at least one m ^2A is an integer from 2 to 7 or at least two m ^2A are integers from 1 to 7, and q ^{A is} independently 0 or 1).  A composition comprising one or more selected from the group consisting of a compound according to any one of claims 1 to 6 and a resin according to any one of claims 7 to 9.    The composition of claim 10, further comprising a solvent.    The composition of claim 10 or 11, further comprising an acid generator.    The composition of any one of claims 10 to 12, further comprising a crosslinking agent.    The composition of claim 13, wherein the crosslinking agent is selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, a melamine compound, a guanamine compound, and a glycol urea. At least one of a compound, a urea compound, an isocyanate compound, and an azide compound.    The composition of claim 13 or 14, wherein the aforementioned crosslinking agent has at least one allyl group.    The composition according to any one of claims 13 to 15, wherein the content of the crosslinking agent is 0.1 to 50% by mass based on the total mass of the solid component.    The composition according to any one of claims 13 to 15, further comprising a crosslinking accelerator.    The composition of claim 17, wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organophosphines, and Lewis acids.    The composition of claim 17, wherein the content of the crosslinking accelerator is 0.1 to 5% by mass based on the total mass of the solid component.    The composition of any one of claims 10 to 12, further comprising a radical polymerization initiator.    The composition according to any one of claims 10 to 12, wherein the radical polymerization initiator is selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator. At least one of the groups.    The composition according to any one of claims 10 to 12, wherein the content of the radical polymerization initiator is 0.05 to 25% by mass based on the total mass of the solid component.    The composition according to any one of claims 10 to 12, which is used for film formation for lithography.    The composition according to any one of claims 10 to 12, which is used for the formation of a permanent film of a resist.    The composition of any one of claims 10 to 22 for use in the formation of optical parts.    A method for forming a resist pattern, comprising the step of forming a photoresist layer on a substrate using a composition as claimed in claim 23, irradiating radiation in a predetermined region of the photoresist layer, and performing development.    A method for forming a resist pattern, comprising: forming an underlayer film on a substrate using the composition of claim 23, forming at least one photoresist layer on the underlayer film, and irradiating the predetermined region of the photoresist layer Radiation and the steps of imaging.    A circuit pattern forming method, characterized in that an underlayer film is formed on a substrate using a composition as claimed in claim 23, and an intermediate layer film is formed on the underlayer film using a resist interlayer film material, and at least the intermediate layer film is formed on the intermediate layer film. After one layer of the photoresist layer, radiation is irradiated on a predetermined region of the photoresist layer to develop a resist pattern, and then the resist pattern is used as a mask, and the intermediate layer film is etched to obtain The intermediate layer film pattern is used as an etching mask to etch the underlying film, and the obtained underlying film pattern is used as an etching mask, and a pattern is formed on the substrate by etching the substrate.