JPWO2018097215A1 - Compound, resin, composition, pattern formation method and purification method - Google Patents

Abstract

The present invention is a compound having a specific structure, a resin having a structural unit derived from the compound, various compositions containing the compound and / or the resin, and various methods using the composition.

Description

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

  In the manufacture of semiconductor devices, microfabrication by lithography using a photoresist material is performed, but in recent years, further miniaturization by a pattern rule has been demanded as LSI is highly integrated and increased in speed. Lithography using light exposure, which is currently used as a general-purpose technology, is approaching the essential resolution limit derived from the wavelength of the light source.

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

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

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

Recently, there is a demand for forming a resist underlayer film for lithography on a work layer having a complicated shape, and there is a demand for a resist underlayer film material that can form an underlayer film excellent in embedding properties and film surface flatness. Yes.

  In addition, regarding the formation method of the intermediate layer used in the formation of the resist underlayer film in the three-layer process, for example, a silicon nitride film formation method (for example, see Patent Document 4) or a silicon nitride film CVD formation method (for example, , See Patent Document 5). As an intermediate layer material for a three-layer process, a material containing a silsesquioxane-based silicon compound is known (see, for example, Patent Documents 6 and 7).

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

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

JP 2004-177668 A JP 2004-271838 A JP-A-2005-250434 JP 2002-334869 A International Publication No. 2004/066377 JP 2007-226170 A JP 2007-226204 A International Publication No. 2013/024779 JP 2010-138393 A Japanese Patent Laying-Open No. 2015-174877 International Publication No. 2014/123005

  As described above, a number of materials for forming a lower layer film for lithography have been proposed in the past. However, high solvent solubility, heat resistance, and etching resistance compatible with wet processes such as spin coating and screen printing are compatible at a high level. There is nothing that has been made, and the development of new materials is required.

  Conventionally, a number of compositions for optical members have been proposed, but none of them has both high heat resistance, transparency and refractive index, and development of new materials is required.

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

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

That is, the present invention is as follows.
[1] A compound represented by the following formula (A).
(In the formula (A), R ^Y is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms,
R ^Z is an m-valent group having 3 to 60 carbon atoms including a cyclic alkyl group having 3 to 30 carbon atoms,
R ^T is each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. An aryl group, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, and a carboxyl group A group, a thiol group, a group in which a hydrogen atom of a hydroxyl group is substituted with an acid dissociable group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group have an ether bond, a ketone bond, or an ester bond. May contain,
Here, at least one of ^RT is a hydroxyl group,
n is each independently an integer of 0 to 8, wherein at least one of n is an integer of 1 to 8,
m is an integer of 1 to 4,
k is each independently an integer of 0-2. )
[2] The compound according to [1], wherein the compound represented by the formula (A) is a compound represented by the following formula (1).
(In the formula (1), R ^Y , R ^Z , m and k have the same meaning as described in the above formula (A).
R ^3A is each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. An aryl group, an optionally substituted alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxyl group, or a thiol group,
R ^4A is each independently a hydrogen atom or an acid dissociable group,
Here, at least one of R ^4A is a hydrogen atom,
m ^6A is each independently an integer of 0 to 7. )
[3] The compound according to [2], wherein the compound represented by the formula (1) is a compound represented by the following formula (1 ′).
(In formula (1 ′), R ^Z has the same meaning as described in formula (A).)
[4] The compound according to [3], wherein the compound represented by the formula (1 ′) is a compound represented by the following formula (2).
[5] The compound according to [4], wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1) or the formula (2-2).
[6] A resin having a structural unit derived from the compound according to any one of [1] to [5].
[7] A composition comprising at least one selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6].
[8] A composition for forming an optical part, comprising at least one selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6].
[9] A film-forming composition for lithography containing at least one selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6].
[10] A resist composition comprising at least one selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6].
[11] The resist composition according to [10], further including a solvent.
[12] The resist composition according to [10] or [11], further including an acid generator.
[13] The resist composition according to any one of [10] to [12], further including an acid diffusion controller.
[14] A step of forming a resist film on the substrate using the resist composition according to any one of [10] to [13];
Exposing at least a portion of the formed resist film;
And developing the exposed resist film to form a resist pattern.
[15] One or more components (A) selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6];
A diazonaphthoquinone photoactive compound (B);
A radiation-sensitive composition containing a solvent,
The content of the solvent is 20 to 99% by mass with respect to 100% by mass of the total amount of the radiation-sensitive composition,
The radiation sensitive composition whose content of components other than the said solvent is 1-80 mass% with respect to 100 mass% of the total amount of the said radiation sensitive composition.
[16] Content ratio ((A)) of said component (A), said diazonaphthoquinone photoactive compound (B), and other optional component (D) optionally contained in said radiation-sensitive composition / (B) / (D)) is 15 to 99% by mass / 99 to 1% by mass / 0 to 98% by mass with respect to 100% by mass of the solid content of the radiation-sensitive composition, [15 ] The radiation sensitive composition of description.
[17] The radiation-sensitive composition according to [15] or [16], wherein an amorphous film can be formed by spin coating.
[18] A method for producing an amorphous film, comprising a step of forming an amorphous film on a substrate using the radiation-sensitive composition according to any one of [15] to [17].
[19] A step of forming a resist film on a substrate using the radiation-sensitive composition according to any one of [15] to [17],
Exposing at least a portion of the formed resist film;
A resist pattern forming method including a step of developing the exposed resist film to form a resist pattern.
[20] A material for forming an underlayer film for lithography, comprising at least one selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6].
[21] The material for forming a lower layer film for lithography according to [20],
A composition for forming a lower layer film for lithography, comprising a solvent.
[22] The composition for forming a lower layer film for lithography according to the above [21], further comprising an acid generator.
[23] The composition for forming a lower layer film for lithography according to [21] or [22], further including a crosslinking agent.
[24] A method for producing an underlayer film for lithography, comprising a step of forming an underlayer film on a substrate using the composition for forming an underlayer film for lithography according to any one of [21] to [23] .
[25] A step of forming an underlayer film on a substrate using the composition for forming an underlayer film for lithography according to any one of [21] to [23],
Forming at least one photoresist layer on the lower layer film;
Irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern.
[26] A step of forming an underlayer film on a substrate using the composition for forming an underlayer film for lithography according to any one of [21] to [23],
Forming an intermediate layer film on the lower layer film using a resist intermediate layer film material containing silicon atoms;
Forming at least one photoresist layer on the intermediate layer film;
Irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern; and
Etching the intermediate layer film using the resist pattern as a mask to form an intermediate layer film pattern;
Etching the lower layer film using the intermediate layer film pattern as an etching mask to form a lower layer film pattern; and
Etching the substrate using the lower layer film pattern as an etching mask to form a pattern on the substrate.
[27] One or more types selected from the group consisting of the compound according to any one of [1] to [5] and the resin according to [6] are dissolved in a solvent to obtain a solution (S). Obtaining a step;
A first extraction step of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the compound and / or the resin,
A purification method, wherein the solvent used in the step of obtaining the solution (S) includes a solvent that is immiscible with water.
[28] The acidic aqueous solution is a mineral acid aqueous solution or an organic acid aqueous solution,
The mineral acid aqueous solution is a mineral acid aqueous solution in which at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid is dissolved in water;
The organic acid aqueous solution is a group consisting of acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid. The purification method according to [27] above, which is an organic acid aqueous solution in which at least one selected from the above is dissolved in water.
[29] The solvent immiscible with water is at least one solvent selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethyl acetate. [27] or the purification method according to [28].
[30] After the first extraction step, the solution phase containing the compound and / or the resin is further brought into contact with water to include a second extraction step of extracting impurities in the compound and / or the resin, [27] The purification method according to any one of [29].

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

  Hereinafter, an embodiment of the present invention (hereinafter, also simply referred to as “this embodiment”) will be described. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

[Compound represented by Formula (A)]
The compound of the present embodiment is a compound represented by the following formula (A).
(In the formula (A), R ^Y is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms,
R ^Z is an m-valent group having 3 to 60 carbon atoms including a cyclic alkyl group having 3 to 30 carbon atoms,
R ^T is each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. An aryl group, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, and a carboxyl group A group, a thiol group, a group in which a hydrogen atom of a hydroxyl group is substituted with an acid dissociable group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group have an ether bond, a ketone bond, or an ester bond. May contain,
Here, at least one of ^RT is a hydroxyl group,
n is each independently an integer of 0 to 8, wherein at least one of n is an integer of 1 to 8,
m is an integer of 1 to 4,
k is an integer of 0-2 each independently. )

R ^Z in the above formula (A) is an m-valent group having 3 to 60 carbon atoms including a cyclic alkyl group having 3 to 30 carbon atoms. The m-valent group is a linear, branched or cyclic alkyl group having 3 to 60 carbon atoms which may have a substituent containing a cyclic alkyl group having 3 to 30 carbon atoms, and 3 to 3 carbon atoms. A C3-C60 linear, branched or cyclic alkylene group which may have a substituent containing 30 cyclic alkyl groups, a substituent containing a C3-C30 cyclic alkyl group A C3-C60 linear, branched or cyclic alkanetriyl group which may optionally have a substituent containing a C3-C30 cyclic alkyl group. , Branched or cyclic alkanetetrayl group, a monovalent aromatic group having 9 to 60 carbon atoms which may have a substituent containing a cyclic alkyl group having 3 to 30 carbon atoms, 3 to 30 carbon atoms Of 9 to 60 carbon atoms which may have a substituent containing a cyclic alkyl group of An aromatic group, a trivalent aromatic group having 9 to 60 carbon atoms which may have a substituent containing a cyclic alkyl group having 3 to 30 carbon atoms, and a substituent containing a cyclic alkyl group having 3 to 30 carbon atoms. It represents a tetravalent aromatic group having 9 to 60 carbon atoms which may be present.
Here, about the cyclic alkyl group containing a C3-C30 cyclic alkyl group, the bridged alicyclic alkyl group containing a C3-C30 cyclic alkyl group is also contained. The m-valent group may have a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms.
As for the cyclic alkyl group, a bridged alicyclic alkyl group is also included.
The compounds of this embodiment, by the above formula (A) in the R ^Z is an m-valent group having 3 to 60 carbon atoms, including cyclic alkyl group having 3 to 30 carbon atoms as described above, high heat resistance Moreover, a good resist pattern shape can be imparted, and furthermore, the etching resistance is also excellent.

  As the m-valent group, from the viewpoint of flatness, a linear, branched or cyclic alkyl having 3 to 60 carbon atoms which may have a substituent containing a cyclic alkyl group having 3 to 30 carbon atoms. A linear, branched or cyclic alkylene group having 3 to 60 carbon atoms and a cyclic alkyl group having 3 to 30 carbon atoms, which may have a substituent containing a cyclic alkyl group having 3 to 30 carbon atoms. A monovalent aromatic group having 9 to 60 carbon atoms, which may have a substituent, and a substituent having 9 to 60 carbon atoms which may have a substituent containing a cyclic alkyl group having 3 to 30 carbon atoms. A valent aromatic group is preferred.

  Although it does not specifically limit as a C3-C60 monovalent group which may have a substituent containing the said C3-C30 cyclic alkyl group, For example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group Cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclooctadecyl group, adamantyl group, cyclohexylphenyl group, cyclohexylnaphthyl group, methylcyclohexylphenyl group, ethylcyclohexylphenyl group, propylcyclohexylphenyl group, A pentylcyclohexylphenyl group, a cyclopropylmethyl group, a cyclohexylmethyl group, an adamantylmethyl group and the like can be mentioned.

  Although it does not specifically limit as a C3-C60 bivalent group which may have a substituent containing the said C3-C30 cyclic alkyl group, For example, a cyclopropylene group, a cyclobutylene group, cyclo Pentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cyclooctadecylene group, adamantylene group, cyclohexylphenylene group, cyclopropyldimethylene group, cyclohexyldimethylene group, adamantyldimethylene Groups and the like.

  Although it does not specifically limit as a C3-C60 trivalent group which may have a substituent containing the said C3-C30 cyclic alkyl group, For example, a cyclopropane triyl group, cyclobutane triyl, for example Group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group, cyclooctadecanetriyl group, cyclohexylbenzenetriyl group, etc. It is done.

  Although it does not specifically limit as a C3-C60 tetravalent group which may have a substituent containing the said C3-C30 cyclic alkyl group, For example, a cyclopropane tetrayl group, cyclobutane tetrayl, for example Group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group, cyclooctadecanetetrayl group, cyclohexylbenzenetetrayl group, cyclo Examples thereof include a propanetetramethylene group, a cyclohexanetetramethylene group, an adamantanetetramethylene group, and a cyclohexylbenzenetetramethylene group.

  Among these, from the viewpoint of heat resistance, a cyclohexylphenyl group, a propylcyclohexylphenyl group, a cyclohexylnaphthyl group, a bicyclohexyl group, and a cyclohexanedimethyl group are preferable. Among these, a cyclohexylphenyl group is preferable from the viewpoint of availability of raw materials.

R ^Y in the above formula (A) is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.

R ^Y in the above formula (A) is each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms which may have a substituent. The alkyl group and the aryl group may contain an ether bond, a ketone bond or an ester bond.

R ^T in the above formula (A) is each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms which may have a substituent. , An optionally substituted alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxyl group, a thiol group, a group in which a hydrogen atom of a hydroxyl group is substituted with an acid dissociable group, and a hydroxyl group A substituent selected from the group consisting of Here, at least one of ^RT is a hydroxyl group. N is each independently an integer of 0 to 8, wherein at least one of n is an integer of 1 to 8, m is an integer of 1 to 4, and k is each independently And it is an integer of 0-2.

In this specification, an acid-dissociable group refers to a characteristic group that is cleaved in the presence of an acid to cause a change such as an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. A phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable. The acid dissociable group may be appropriately selected from those proposed for hydroxystyrene resins, (meth) acrylic resins and the like used in chemically amplified resist compositions for KrF and ArF. it can. Although not limited, for example, an acid dissociable group described in JP 2012-136520 A is used.

Since the compound of this embodiment has the above structure, it has high heat resistance and high solvent solubility. Moreover, it is preferable that the compound of this embodiment is a compound represented by following formula (1) from the viewpoint of the solubility to a solvent, and heat resistance.
(In the formula (1), R ^Z , R ^Y , m and k have the same meanings as described in the formula (A).
R ^3A is each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. An aryl group, an optionally substituted alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxyl group, or a thiol group,
R ^4A is each independently a hydrogen atom or an acid dissociable group,
Here, at least one of R ^4A is a hydrogen atom,
m ^6A is each independently an integer of 0 to 7. )

Further, from the viewpoint of solubility in a solvent and heat resistance, in the present embodiment, the compound represented by the formula (1) is preferably a compound represented by the following formula (1 ′).
(In formula (1 ′), R ^Z has the same meaning as described in formula (A).)

Furthermore, from the viewpoint of heat resistance and solubility in an organic solvent, in the present embodiment, the compound represented by (1 ′) is preferably a compound represented by the following formula (2).

Furthermore, from the viewpoint of heat resistance and solubility in an organic solvent, specific examples of the compound represented by the formula (2) are exemplified below in the present embodiment, but are not limited thereto. Moreover, it is preferable that it is a compound represented by a following formula (2-1) or a formula (2-2).

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

In the formula, R ^{T ′} has the same meaning as R ^T described in the formula (A), and m is each independently an integer of 1 to 6.

In the formula, R ^{T ′} has the same meaning as R ^T described in the formula (A), and m is each independently an integer of 1 to 6.

In the above formula, R ^{Z ′} has the same meaning as R ^Z described in the formula (A). Furthermore, each R ^4A is independently a hydrogen atom or an acid dissociable group, and at least one of the OR ^4A is a hydroxyl group.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Further, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1 to 5.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Further, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1 to 9.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Further, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1 to 7.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Further, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1 to 9.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Further, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1 to 7.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Further, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1 to 4.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Furthermore, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1-6.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Further, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1 to 8.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Further, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1 to 8.

In the above formula, ^{RT ′} is a cyclic alkyl group having 3 to 30 carbon atoms. Further, each R ^4A is independently a hydrogen atom or an acid dissociable group, at least one of the OR ^4A is a hydroxyl group, and m is an integer of 1 to 3.
Furthermore, the compound represented by the formula (A) is preferably a compound having the following structure from the viewpoint of etching resistance.

In the formula, R ^0A has the same meaning as R ^Y explained in the formula (A), R ^{1A ′} has the same meaning as R ^Z explained in the formula (A), and R ¹⁰ and R ¹¹ are the same as those in the formula. It is synonymous with R ^4A described in (1).

In the formula, R ^0A has the same meaning as R ^Y explained in the formula (A), R ^{1A ′} has the same meaning as R ^Z explained in the formula (A), and R ¹⁰ and R ¹¹ are the same as those in the formula. It is synonymous with R ^4A described in (1). R ¹⁴ is a cyclic alkyl group having 3 to 30 carbon atoms, and m ¹⁴ is each independently an integer of 0 to 5.

In the formula, R ¹⁰ and R ¹¹ have the same meaning as R ^4A described in the formula (1), and R ¹⁵ is a C 3-30 cyclic alkyl group.

In the formula, R ¹⁰ and R ¹¹ have the same meaning as R ^4A described in the formula (1), and R ¹⁶ is a group containing a cyclic alkyl group having 3 to 30 carbon atoms.

In the formula, R ¹⁰ and R ¹¹ have the same meaning as R ^4A described in the formula (1), and R ¹⁴ is a cyclic alkyl group having 3 to 30 carbon atoms. m14 ^' is an integer of 0-4 each independently. However, at least 1 m14 ^' is an integer of 1-4.

In the formula, R ¹⁰ and R ¹¹ have the same meaning as R ^4A described in the formula (1), and R ¹⁴ is a cyclic alkyl group having 3 to 30 carbon atoms. m14 ^' is an integer of 1-4.

In the formula, R ¹⁰ and R ¹¹ have the same meaning as R ^4A described in the formula (1), and R ¹⁴ is a cyclic alkyl group having 3 to 30 carbon atoms. m14 ^' is an integer of 0-4 each independently. However, at least 1 m14 ^' is an integer of 1-4.

In the above formula, R ¹⁰ and R ¹¹ are synonymous with R ^4A described in formula (1), and R ¹⁴ is a cyclic alkyl group having 3 to 30 carbon atoms. m ^{14 ′} is each independently an integer of 1 to 4.

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

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

In the formula, R ^0A has the same meaning as R ^Y explained in the formula (A), R ^{1A ′} has the same meaning as R ^Z explained in the formula (A), and R ¹⁰ , R ¹¹ and R ¹³ are , ^Which has the same meaning as R ^4A described in Formula (1). The compound represented by the formula is preferably a compound having a xanthene skeleton from the viewpoint of heat resistance.

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

[Production Method of Compound Represented by Formula (A)]
The compound represented by the formula (A) of the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited. For example, a compound represented by the above general formula (A) is obtained by polycondensation reaction of naphthols with aldehydes or ketones corresponding to the desired compound structure under an acid catalyst under normal pressure. be able to. Moreover, it can also carry out under pressure as needed.

  Examples of the naphthols include, but are not limited to, naphthol, methyl naphthol, methoxynaphthalene, naphthalene diol, naphthalene triol, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is more preferable to use naphthalenediol and naphthalenetriol from the viewpoint that a xanthene structure can be easily formed.

  Examples of the aldehydes include cyclopropyl aldehyde, cyclobutyraldehyde, cyclohexyl aldehyde, cyclodecyl aldehyde, cycloundecyl aldehyde, cyclopropyl benzaldehyde, cyclobutyl benzaldehyde, cyclohexyl benzaldehyde, cyclodecyl benzaldehyde, cycloundecyl benzaldehyde and the like. However, it is not particularly limited to these. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use cyclohexylbenzaldehyde, cyclodecylbenzaldehyde, cycloundecylbenzaldehyde and the like from the viewpoint of providing high heat resistance.

  Examples of the ketones include, but are not limited to, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, cycloundecanone, and adamantanone. These can be used alone or in combination of two or more. Among these, it is preferable to use cyclohexanone or cycloundecanone from the viewpoint of giving high heat resistance.

  The acid catalyst used in the above reaction can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known. Specific examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid; oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid. Organic acids such as acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid; zinc chloride, aluminum chloride Lewis acids such as iron chloride and boron trifluoride; solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid, but are not particularly limited thereto. Among these, an organic acid and a solid acid are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as availability and ease of handling. In addition, about an acid catalyst, 1 type can be used individually or in combination of 2 or more types. The amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst to be used, and further the reaction conditions, and is not particularly limited. It is preferable that it is a mass part.

  In the case of the above reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction between aldehydes or ketones to be used and phenols proceeds, and can be appropriately selected from known ones. For example, water, methanol , Ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, or a mixed solvent thereof. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types. Moreover, the usage-amount of these solvent can be suitably set according to the raw material to be used, the kind of acid catalyst to be used, and also reaction conditions. Although it does not specifically limit as the usage-amount of the said solvent, It is preferable that it is the range of 0-2000 mass parts with respect to 100 mass parts of reaction raw materials. Furthermore, the reaction temperature in the above reaction can be appropriately selected according to the reactivity of the reaction raw materials. Although it does not specifically limit as said reaction temperature, Usually, it is preferable that it is the range of 10-200 degreeC. In order to form a xanthene structure or a thioxanthene structure as a compound having a structure represented by the general formula (A) of the present embodiment, the reaction temperature is preferably higher, specifically in the range of 60 to 200 ° C. Is preferred. The reaction method can be appropriately selected from known methods, and is not particularly limited. However, phenols, aldehydes or ketones, a method in which an acid catalyst is charged at once, phenols, aldehydes or ketones are used. Can be added dropwise in the presence of an acid catalyst. After completion of the polycondensation reaction, the obtained compound can be isolated according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, acid catalysts, etc. existing in the system, a general method such as raising the temperature of the reaction kettle to 130 to 230 ° C. and removing volatile components at about 1 to 50 mmHg, etc. By taking it, the target compound can be obtained.

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

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

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

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

[Resin having a structural unit derived from the compound represented by the formula (A)]
The resin of the present embodiment is a resin having a structural unit derived from the compound represented by the above formula (A) (hereinafter also referred to as “the compound of the present embodiment”). The compound represented by the above formula (A) can be used as it is as a film-forming composition for lithography. Moreover, it can be used also as resin which has a structural unit derived from the compound represented by the said Formula (A). The resin having a structural unit derived from the compound represented by the formula (A) is represented by a resin having a structural unit derived from the compound represented by the formula (1) and the formula (1 ′). A resin having a structural unit derived from the compound represented by formula (2), and a resin having a structural unit derived from the compound represented by formula (2). It can be read as “compound represented by 1)”, “compound represented by formula (1 ′)”, and “compound represented by formula (2)”.

[Method for Producing Resin Having Structural Unit Derived from Compound Represented by Formula (A)]
The resin of the present embodiment is obtained, for example, by reacting a compound represented by the above formula (A) with a compound having a crosslinking reaction.

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

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

  Here, as an aldehyde used when novolak-forming the compound represented by the above formula (A), for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Examples thereof include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural. Among these, formaldehyde is more preferable. In addition, these aldehydes can be used individually by 1 type or in combination of 2 or more types. Moreover, the usage-amount of the said aldehydes is although it does not specifically limit, 0.2-5 mol is preferable with respect to 1 mol of compounds represented by the said Formula (A), More preferably, it is 0.5-2 mol. is there.

  In the condensation reaction between the compound represented by the above formula (A) and the aldehyde, an acid catalyst may be used. The acid catalyst used here can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids, organic acids, Lewis acids, and solid acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, Malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfone Acids, organic acids such as naphthalene sulfonic acid and naphthalene disulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; or silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Solid acids and the like can be mentioned, but are not particularly limited thereto. Of these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of production such as availability and ease of handling. In addition, about an acid catalyst, 1 type can be used individually or in combination of 2 or more types.

  The amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst to be used, and further the reaction conditions, and is not particularly limited. It is preferable that it is a mass part.

  However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, In the case of a copolymerization reaction with a compound having a non-conjugated double bond such as α-pinene, β-pinene and limonene, aldehydes are not necessarily required.

In the condensation reaction between the compound represented by the above formula (A) and the aldehyde, a reaction solvent may be used. The reaction solvent in this polycondensation can be appropriately selected from known solvents and is not particularly limited. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. Illustrated. In addition, a reaction solvent can be used individually by 1 type or in combination of 2 or more types.

  The amount of these reaction solvents used can be appropriately set according to the raw materials used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 mass with respect to 100 parts by mass of the reaction raw materials. The range of parts is preferred. Furthermore, reaction temperature can be suitably selected according to the reactivity of the reaction raw material, and although it does not specifically limit, it is the range of 10-200 degreeC normally. In addition, the reaction method can select and use a well-known method suitably, Although it does not specifically limit, The method of charging the compound represented by the said Formula (A), aldehydes, and a catalyst collectively, said Formula (A) There is a method in which a compound or an aldehyde represented by (2) is dropped in the presence of a catalyst.

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

  Here, the resin in the present embodiment may be a homopolymer of the compound represented by the above formula (A), or may be a copolymer with other phenols. Examples of the copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Although propylphenol, pyrogallol, thymol, etc. are mentioned, it is not specifically limited to these.

  Further, the resin in the present embodiment may be copolymerized with a polymerizable monomer other than the above-described other phenols. Examples of the copolymerization monomer include naphthol, methyl naphthol, methoxy naphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene. , Norbornadiene, vinylnorbornaene, pinene, limonene and the like, but are not particularly limited thereto. In addition, even if resin in this embodiment is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the said Formula (A), and the phenol mentioned above, the said Formula ( Even if it is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by A) and the above-mentioned copolymerization monomer, the compound represented by the above formula (A) and the above-described phenols And a terpolymer (for example, 3-4 quaternary) copolymer of the above-mentioned copolymerization monomer.

  In addition, although the molecular weight of resin in this embodiment is not specifically limited, It is preferable that the weight average molecular weights (Mw) of polystyrene conversion are 500-30,000, More preferably, it is 750-20,000. Further, from the viewpoint of increasing the crosslinking efficiency and suppressing the volatile components in the baking, the resin in this embodiment has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) in the range of 1.2 to 7. preferable. In addition, said Mn can be calculated | required by the method as described in the Example mentioned later.

[Composition]
The composition of this embodiment contains 1 or more types of substances chosen from the group which consists of resin which has a compound represented by the said Formula (A), and the structural unit derived from this compound. Moreover, the composition of this embodiment may contain both the compound of this embodiment and the resin of this embodiment. Hereinafter, “one or more selected from the group consisting of a compound represented by the above formula (A) and a resin having a structural unit derived from the compound” is referred to as “the compound and / or resin of this embodiment” or “component. (A) ".

[Composition for optical component formation]
The composition for forming an optical component according to this embodiment contains one or more selected from the group consisting of a compound represented by the above formula (A) and a resin having a structural unit derived from the compound. Moreover, the composition for optical component formation of this embodiment may contain both the compound of this embodiment and the resin of this embodiment. Here, the “optical component” means a film-like or sheet-like component, a plastic lens (prism lens, lenticular lens, microlens, Fresnel lens, viewing angle control lens, contrast enhancement lens, etc.), retardation film, An electromagnetic shielding film, a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide. The compounds and resins of this embodiment are useful for these optical component forming applications.

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

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

  Moreover, it is preferable that the resist composition of this embodiment contains a solvent. Although it does not specifically limit as a solvent, For example, ethylene glycol monoalkyl ether acetates, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono -Propylene glycol such as n-butyl ether acetate Cole monoalkyl ether acetates; 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. Lactate esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyrate Other esters such as acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN); N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N -Amides such as methylpyrrolidone; lactones such as γ-lactone can be mentioned, but there is no particular limitation. These solvents can be used alone or in combination of two or more.

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

  In the present embodiment, the amount of the solid component and the amount of the solvent are not particularly limited, but 1 to 80% by weight of the solid component and 20 to 99% by weight of the solvent with respect to 100% by weight of the total amount of the solid component and the solvent. %, More preferably 1 to 50% by weight of the solid component and 50 to 99% by weight of the solvent, more preferably 2 to 40% by weight of the solid component and 60 to 98% by weight of the solvent, particularly preferably the solid component. 2 to 10% by mass and solvent 90 to 98% by mass.

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

[Acid generator (C)]
In the resist composition of this embodiment, acid is generated directly or indirectly by irradiation with radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray and ion beam. It is preferable to include one or more acid generators (C). Although an acid generator (C) is not specifically limited, For example, the thing as described in international publication 2013/024778 can be used. The acid generator (C) can be used alone or in combination of two or more.

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

[Acid crosslinking agent (G)]
In this embodiment, it is preferable to include one or more acid crosslinking agents (G). The acid crosslinking agent (G) is a compound capable of crosslinking the component (A) in the molecule or between molecules in the presence of the acid generated from the acid generator (C). Examples of such an acid crosslinking agent (G) include a compound having one or more groups capable of crosslinking the component (A) (hereinafter referred to as “crosslinkable group”).

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

  Although it does not specifically limit as an acid crosslinking agent (G) which has the said crosslinkable group, For example, what is described in international publication 2013/024778 can be used. The acid crosslinking agent (G) can be used alone or in combination of two or more.

  In the present embodiment, the amount of the acid crosslinking agent (G) used is preferably 0.5 to 49% by mass, more preferably 0.5 to 40% by mass, and still more preferably 1 to 30% by mass based on the total weight of the solid component. 2-20 mass% is especially preferable. When the blending ratio of the acid cross-linking agent (G) is 0.5% by mass or more, the effect of suppressing the solubility of the resist film in an alkaline developer is improved, the remaining film ratio is decreased, pattern swelling and meandering are caused. It is preferable because it can be prevented from occurring. On the other hand, when it is 50% by mass or less, it is preferable because a decrease in heat resistance as a resist can be suppressed.

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

  Although it does not specifically limit as said acid diffusion control agent (E), For example, the thing as described in international publication 2013/024778 can be used. The acid diffusion controller (E) can be used alone or in combination of two or more.

  The blending amount of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, further preferably 0.01 to 5% by mass, based on the total weight of the solid component. 0.01 to 3% by mass is particularly preferable. Within the above range, it is possible to prevent degradation in resolution, pattern shape, dimensional fidelity, and the like. Furthermore, even if the holding time from electron beam irradiation to heating after radiation irradiation becomes longer, the shape of the pattern upper layer portion does not deteriorate. Moreover, the fall of a sensitivity, the developability of an unexposed part, etc. can be prevented as a compounding quantity is 10 mass% or less. Further, by using such an acid diffusion control agent, the storage stability of the resist composition is improved and the resolution is improved, and also due to fluctuations in the holding time before irradiation and the holding time after irradiation. Changes in the line width of the resist pattern can be suppressed, and the process stability is extremely excellent.

[Other components (F)]
In the resist composition of the present embodiment, as the other component (F), a dissolution accelerator, a dissolution controller, a sensitizer, a surfactant, an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof, as necessary. 1 type, or 2 or more types can be added.

[Solution Accelerator]
The low-molecular-weight dissolution accelerator increases the solubility of the compound represented by the formula (A) in the developing solution when it is too low, and appropriately increases the dissolution rate of the compound during development. It can be used as needed. Examples of the dissolution accelerator include low molecular weight phenolic compounds, and examples thereof include bisphenols and tris (hydroxyphenyl) methane. These dissolution promoters can be used alone or in admixture of two or more.

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

[Solution control agent]
The dissolution control agent is a component having an action of appropriately reducing the dissolution rate during development by controlling the solubility when the solubility of the compound represented by the formula (A) in the developer is too high. As such a dissolution control agent, those that do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable.

Although it does not specifically limit as a dissolution control agent, For example, Aromatic hydrocarbons, such as phenanthrene, anthracene, and acenaphthene; Ketones, such as acetophenone, benzophenone, and phenyl naphthyl ketone; Methyl phenyl sulfone, diphenyl sulfone, dinaphthyl sulfone, etc. Examples include sulfones. These dissolution control agents can be used alone or in combination of two or more.
The blending amount of the dissolution control agent is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass based on the total weight of the solid components. Is more preferable, and 0% by mass is particularly preferable.

[Sensitizer]
The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (C), thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist. It is a component to be made. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more.

  Although the compounding quantity of a sensitizer is suitably adjusted according to the kind of said compound to be used, 0-49 mass% of a solid component total weight is preferable, 0-5 mass% is more preferable, 0-1 mass% is preferable. More preferred is 0% by mass.

[Surfactant]
The surfactant is a component having an action of improving the coating property and striation of the resist composition of the present embodiment, the developing property of the resist, and the like. Such a surfactant may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant. A preferred surfactant is a nonionic surfactant. The nonionic surfactant has a good affinity with the solvent used in the production of the resist composition and is more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the like, but are not particularly limited. Although it does not specifically limit as a commercial item, The following brand names, for example, F top (made by Gemco), MegaFac (made by Dainippon Ink and Chemicals), Florard (made by Sumitomo 3M), Asahi Guard, Surflon ( As mentioned above, Asahi Glass Co., Ltd., Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), etc.

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

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

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

[Other additives other than the above-mentioned additives (dissolution accelerators, dissolution control agents, sensitizers, surfactants, organic carboxylic acids or phosphorus oxo acids or derivatives thereof)]
Furthermore, in the resist composition of the present embodiment, if necessary, one kind of additive other than the above-mentioned dissolution control agent, sensitizer, surfactant, and organic carboxylic acid or phosphorus oxo acid or derivative thereof. Or 2 or more types can be mix | blended. Examples of such additives include dyes, pigments, and adhesion aids. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Further, the other additives are not particularly limited, but examples thereof include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone and the like. Can do.

  In the resist composition of this embodiment, the total amount of the optional component (F) is 0 to 99% by mass, preferably 0 to 49% by mass, more preferably 0 to 10% by mass, based on the total weight of the solid component. -5% by mass is more preferable, 0-1% by mass is more preferable, and 0% by mass is particularly preferable.

[Blend ratio of each component in resist composition]
In the resist composition of this embodiment, the content of the compound and / or resin of this embodiment is not particularly limited, but the total mass of the solid component (compound represented by formula (A), represented by formula (A)). Resins containing the above compound as a constituent, acid generator (C), acid crosslinking agent (G), acid diffusion controller (E), and other components (F) (also referred to as “optional component (F)”), etc. 50-99.4% by mass of the total of solid components including the optionally used components, the same applies hereinafter), more preferably 55-90% by mass, still more preferably 60-80% by mass, Especially preferably, it is 60-70 mass%. In the case of the above content, the resolution is further improved and the line edge roughness (LER) is further reduced. In addition, when it contains both the compound and resin of this embodiment, the said content is the total amount of the compound and resin of this embodiment.

  In the resist composition of the present embodiment, the compound and / or resin (component (A)), acid generator (C), acid crosslinking agent (G), acid diffusion controller (E), optional component (of the present embodiment) The content ratio of (F) (component (A) / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) is 100 mass of the solid content of the resist composition. %, Preferably 50-99.4% by mass / 0.001-49% by mass / 0.5-49% by mass / 0.001-49% by mass / 0-49% by mass, more preferably It is 55-90 mass% / 1-40 mass% / 0.5-40 mass% / 0.01-10 mass% / 0-5 mass%, More preferably, it is 60-80 mass% / 3-30 mass%. / 1 to 30% by mass / 0.01 to 5% by mass / 0 to 1% by mass, particularly preferably 60 to 70% by mass / 10 to 10% by mass. 5 wt% / 2-20 mass% / 0.01-3 mass% / 0% by weight and. The blending ratio of the components is selected from each range so that the sum is 100% by mass. When the above composition is used, the performance such as sensitivity, resolution and developability is excellent. “Solid content” refers to a component excluding the solvent, and “solid content of 100% by mass” refers to 100% by mass of the component excluding the solvent.

  The resist composition of this embodiment is usually prepared by dissolving each component in a solvent at the time of use to make a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, for example, as necessary. The

  The resist composition of this embodiment can contain other resin other than the resin of this embodiment as needed. The resin is not particularly limited. For example, a novolak resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and a heavy polymer containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units. A combination or a derivative thereof may be used. The content of the resin is not particularly limited and is appropriately adjusted according to the type of the component (A) to be used, but is preferably 30 parts by mass or less, more preferably 100 parts by mass of the component (A). It is 10 mass parts or less, More preferably, it is 5 mass parts or less, Most preferably, it is 0 mass part.

[Physical properties of resist composition]
The resist composition of this embodiment can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process. Depending on the type of developer used, either a positive resist pattern or a negative resist pattern can be created.

  In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition of this embodiment at 23 ° C. with respect to the developer is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec. Preferably, 0.0005-5 g / sec is more preferable. When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed to be due to the increase in the contrast of the interface between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer due to the change in solubility of the component (A) before and after exposure. Further, there is an effect of reducing LER and reducing defects.

  In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin coating the resist composition of the present embodiment with respect to the developer at 23 ° C. is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developer and more suitable for a resist. Further, when the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the component (A) is dissolved and LER is reduced. There is also an effect of reducing defects.

  The dissolution rate is determined by immersing an amorphous film in a developer for a predetermined time at 23 ° C., and measuring the film thickness before and after the immersion by a known method such as visual observation, ellipsometer, or quartz crystal microbalance (QCM method). Can be determined.

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

  In the case of a negative resist pattern, the amorphous film formed by spin-coating the resist composition of this embodiment is exposed to a developing solution at 23 ° C. at a portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The dissolution rate is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and further preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumably because the contrast of the interface between the unexposed portion that dissolves in the developer and the exposed portion that does not dissolve in the developer increases due to the change in solubility of the component (A) before and after exposure. Further, there is an effect of reducing LER and reducing defects.

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

  The component (A) contained in the radiation-sensitive composition of the present embodiment is used in combination with a diazonaphthoquinone photoactive compound (B) described later, g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme It is useful as a positive resist substrate that becomes a compound that is easily soluble in a developer by irradiation with ultraviolet rays, electron beams, or X-rays. G-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray does not change the property of component (A) greatly, but diazonaphthoquinone photoactivity is hardly soluble in the developer. By changing the compound (B) into a readily soluble compound, a resist pattern can be formed by a development process.

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

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

  The calorific value of crystallization determined by differential scanning calorimetric analysis of the glass transition temperature of the component (A) contained in the radiation-sensitive composition of the present embodiment is preferably less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further 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 in the above range, it is easy to form an amorphous film by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.

  In this embodiment, the crystallization calorific value, the crystallization temperature, and the glass transition temperature can be determined by differential scanning calorimetry using DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is put into an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 mL / min). After the rapid cooling, the temperature is raised again to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 mL / min). Further, after rapid cooling, the temperature is increased again to 400 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen gas stream (30 mL / min). The temperature at the midpoint of the step difference of the baseline that has changed in a step shape (where the specific heat has changed to half) is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature. The calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.

  The component (A) contained in the radiation-sensitive composition of the present embodiment is 100 or less, preferably 120 ° C. or less, more preferably 130 ° C. or less, further preferably 140 ° C. or less, and particularly preferably 150 ° C. or less under normal pressure. It is preferable that sublimability is low. Low sublimation means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, even more preferably 1% or less, particularly preferably Indicates 0.1% or less. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. In addition, a good pattern shape can be obtained with low roughness.

  Component (A) contained in the radiation-sensitive composition of the present embodiment is propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone , Anisole, butyl acetate, ethyl propionate and ethyl lactate, and a solvent exhibiting the highest solubility in component (A) at 23 ° C., preferably 1% by mass or more, more preferably 5% by mass % Or more, more preferably 10% by mass or more, and even more preferably, a solvent selected from PGMEA, PGME, and CHN and having the highest solubility for component (A) at 23 ° C., 20 More than 20% by mass dissolves, particularly preferably at 23 ° C. with respect to PGMEA. To the solution. By satisfying the above conditions, the semiconductor manufacturing process can be used in actual production.

[Diazonaphthoquinone Photoactive Compound (B)]
The diazonaphthoquinone photoactive compound (B) to be contained in the radiation-sensitive composition of the present embodiment is a diazonaphthoquinone substance containing a polymeric and non-polymeric diazonaphthoquinone photoactive compound, and in general in a positive resist composition, As long as it is used as a photosensitive component (photosensitive agent), one type or two or more types can be arbitrarily selected and used without any limitation.

  As such a photosensitizer, it was obtained by reacting naphthoquinone diazide sulfonic acid chloride, benzoquinone diazide sulfonic acid chloride, etc. with a low molecular compound or a high molecular compound having a functional group capable of condensation reaction with these acid chlorides. Compounds are preferred. Here, the functional group capable of condensing with acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, and a hydroxyl group is particularly preferable. The compound capable of condensing with an acid chloride containing a hydroxyl group is not particularly limited. For example, hydroquinone, resorcin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2 ′, 3,4,6′- Hydroxybenzophenones such as pentahydroxybenzophenone, hydroxyphenylalkanes such as bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane 4,4 ', 3 ", 4" -tetrahydroxy −3,5,3 ′, 5′-tetramethyltriphenylmethane, 4,4 ′, 2 ″, 3 ″, 4 ″ -pentahydroxy-3,5,3 ′, 5′-tetramethyltriphenylmethane, etc. And hydroxytriphenylmethanes.

  Examples of acid chlorides such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-5-sulfonyl chloride and 1,2-naphthoquinone diazide-4-sulfonyl chloride. Can be mentioned.

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

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

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

  Moreover, content of components (solid component) other than a solvent is 1-80 mass% with respect to 100 mass% of total amounts of a radiation sensitive composition, Preferably it is 1-50 mass%, More preferably It is 2-40 mass%, Most preferably, it is 2-10 mass%.

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

  In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment with respect to the developer at 23 ° C. is preferably 5 Å / sec or less, and 0.05 to 5 Å / sec. Is more preferable, and 0.0005-5 g / sec is further more preferable. When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed to be due to the increase in the contrast of the interface between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer due to the change in solubility of the component (A) before and after exposure. Further, there is an effect of reducing LER and reducing defects.

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

  The dissolution rate can be determined by immersing the amorphous film in a developer at a temperature of 23 ° C. for a predetermined time, and measuring the film thickness before and after the immersion by a known method such as visual observation, 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, extreme ultraviolet light, electron beam or X-ray, or 20 to 20 The dissolution rate of the exposed portion after heating at 500 ° C. in the developer at 23 ° C. is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, and even more preferably 100 to 1000 Å / sec. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developer and more suitable for a resist. In addition, when the dissolution rate is 10000 kg / sec or less, the resolution may be improved. This is presumed to be because the micro surface portion of the component (A) is dissolved and LER is reduced. There is also an effect of reducing defects.
In the case of a negative resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or 20 to 20 The dissolution rate of the exposed portion after heating at 500 ° C. in the developer at 23 ° C. is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and further preferably 0.0005 to 5 Å / sec. . When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumably because the contrast of the interface between the unexposed portion that dissolves in the developer and the exposed portion that does not dissolve in the developer increases due to the change in solubility of the component (A) before and after exposure. Further, there is an effect of reducing LER and reducing defects.

[Combination ratio of each component in the radiation-sensitive composition]
In the radiation-sensitive composition of the present embodiment, the content of the component (A) is arbitrarily selected from the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B), and other components (D)). The total of the solid components to be used, the same shall apply hereinafter) is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass. %. When the content of the component (A) is within the above range, the radiation-sensitive composition of this embodiment can obtain a pattern with high sensitivity and small roughness.

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

[Other components (D)]
In the radiation-sensitive composition of the present embodiment, the above-described acid generator, acid crosslinking agent, acid diffusion controller, as components other than the component (A) and the diazonaphthoquinone photoactive compound (B), if necessary, One kind or two or more kinds of various additives such as a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant, an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be added. In addition, in this specification, another component (D) may be called arbitrary component (D).

  Content ratio ((A) / (B) / () of component (A), diazonaphthoquinone photoactive compound (B) and other optional component (D) optionally contained in the radiation-sensitive composition D)) is preferably 1 to 99% by mass / 99 to 1% by mass / 0 to 98% by mass, more preferably 5 to 95% by mass with respect to 100% by mass of the solid content of the radiation-sensitive composition. / 95-5% by mass / 0-49% by mass, more preferably 10-90% by mass / 90-10% by mass / 0-10% by mass, and particularly preferably 20-80% by mass / 80-20%. It is mass% / 0-5 mass%, Most preferably, it is 25-75 mass% / 75-25 mass% / 0 mass%.

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

  The radiation sensitive composition of this embodiment may contain resin other than this embodiment. Examples of such resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units, or these. Derivatives and the like. Although the compounding quantity of these resin is suitably adjusted according to the kind of component (A) to be used, 30 mass parts or less are preferable with respect to 100 mass parts of components (A), More preferably, 10 mass parts or less More preferably, it is 5 parts by mass or less, and particularly preferably 0 part by mass.

[Method of manufacturing amorphous film]
The manufacturing method of the amorphous film of this embodiment includes the process of forming an amorphous film on a board | substrate using the said radiation sensitive composition.

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

[Method of forming resist pattern using resist composition]
A resist pattern forming method using the resist composition of the present embodiment includes a step of forming a resist film on a substrate using the resist composition of the present embodiment described above, and at least a part of the formed resist film. A step of exposing, and a step of developing the exposed resist film to form a resist pattern. The resist pattern in this embodiment can also be formed as an upper 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 is formed by applying the resist composition of the present embodiment on a conventionally known substrate by a coating means such as spin coating, cast coating, roll coating or the like. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, although not particularly limited, for example, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. The material for the wiring pattern is not particularly limited, and examples thereof include copper, aluminum, nickel, and gold. If necessary, an inorganic and / or organic film may be provided on the substrate. The inorganic film is not particularly limited, and examples thereof include an inorganic antireflection film (inorganic BARC). Although it does not specifically limit as an organic film | membrane, For example, an organic antireflection film (organic BARC) is mentioned. Surface treatment with hexamethylene disilazane or the like may be performed.

  Next, the coated substrate is heated as necessary. Although heating conditions change with the compounding composition of a resist composition, etc., 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the resist composition. In this embodiment, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after radiation irradiation.

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

  Although it does not specifically limit as a ketone solvent, For example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone , Phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like.

  The ester solvent is not particularly limited. For example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether Acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. be able to.

  Although it does not specifically limit as alcohol solvent, For example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, alcohols such as n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, and ethylene glycol monomethyl Ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether Ether, triethylene glycol monoethyl ether, and triethylene glycol monoethyl ether and methoxymethyl butanol.

  Although it does not specifically limit as an ether solvent, For example, a dioxane, tetrahydrofuran, etc. other than the said glycol ether solvent are mentioned.

  The amide solvent is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2- Imidazolidinone can be used.

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

  A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than the above or water within the range having performance. However, in order to fully achieve the effects of the present invention, the water content of the developer as a whole is less than 70% by mass, preferably less than 50% by mass, and more preferably less than 30% by mass. Preferably, it is more preferably less than 10% by mass, and it is particularly preferable that it contains substantially no water. That is, the content of the organic solvent with respect to the developer is 30% by mass to 100% by mass, preferably 50% by mass to 100% by mass, and preferably 70% by mass to 100% by mass with respect to the total amount of the developer. More preferably, it is 90 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less, It is especially preferable that it is 95 mass% or more and 100 mass% or less.

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

  In particular, the developer is a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, such as resist pattern resolution and roughness. It is preferable for improving the resist performance.

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

  Specific examples having a vapor pressure of 5 kPa or less include, but are not limited to, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone Ketone solvents such as phenylacetone and methyl isobutyl ketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropio Nate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactate Ester solvents such as pills; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl Alcohol solvents such as alcohol, n-octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl Ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, etc. Ether ether solvents; ether solvents such as tetrahydrofuran; amide solvents of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene, octane And aliphatic hydrocarbon solvents such as decane.

  Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. , Ketone solvents such as phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate; n-butyl alcohol; alcohol solvents such as ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol; ethylene glycol, diethylene glycol Glycol solvents such as triethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol Solvents: N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Amide solvents formamide; aromatic hydrocarbon solvents such as xylene, octane, include aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the developer as necessary.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants are, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, Mention may be made of the surfactants described in US Pat. Nos. 5,360,692, 5,529,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

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

  The development method is not particularly limited. For example, the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), and the developer is raised on the surface of the substrate by surface tension and left stationary for a certain period of time. Development method (paddle method), spraying developer solution onto the substrate surface (spray method), developing solution is continuously applied to the substrate rotating at a constant speed while scanning the developer application nozzle at a constant speed. A method (dynamic dispensing method) or the like can be applied. The time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

  Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.

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

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

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

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

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

  The vapor pressure of the rinsing solution used after development is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, and further, the swelling due to the penetration of the rinsing liquid is further suppressed, and the dimensions in the wafer surface are reduced. Uniformity is improved.

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

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

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

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

  The residual resist pattern after etching can be peeled off with an organic solvent. Although it does not specifically limit as said organic solvent, For example, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) etc. are mentioned. Although it does not specifically limit as said peeling method, For example, the immersion method, a spray system, etc. are mentioned. The wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

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

[Underlayer film forming material for lithography]
The material for forming a lower layer film for lithography of this embodiment contains the compound of this embodiment and / or the resin of this embodiment. The compound of this embodiment and / or the resin of this embodiment is preferably 1 to 100% by mass, and preferably 10 to 100% by mass, in the lower layer film-forming material for lithography, from the viewpoints of coatability and quality stability. More preferably, it is more preferable that it is 50-100 mass%, and it is especially preferable that it is 100 mass%.

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

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

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

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

  Of 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.

  Although content of a solvent is not specifically limited, From a viewpoint on solubility and film formation, it is preferable that it is 100-10,000 mass parts with respect to 100 mass parts of the said lower layer film formation materials, 200-5, More preferably, it is 000 mass parts, and it is further more preferable that it is 200-1,000 mass parts.

[Crosslinking agent]
The composition for forming a lower layer film for lithography of the present embodiment may contain a crosslinking agent as necessary from the viewpoint of suppressing intermixing. Although it does not specifically limit as a crosslinking agent which can be used by this embodiment, For example, the thing of international publication 2013/024779 can be used. In this embodiment, the crosslinking agent can be used alone or in combination of two or more.

  Specific examples of the crosslinking agent that can be used in this embodiment include, for example, phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanates. Examples thereof include, but are not limited to, compounds and azide compounds. These crosslinking agents can be used alone or in combination of two or more. Among these, a benzoxazine compound, an epoxy compound, or a cyanate compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improving etching resistance.

  A well-known thing can be used as said phenolic compound. For example, the phenols are not particularly limited, but other than phenol, alkylphenols such as cresols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalenediols, bisphenol A, Examples thereof include bisphenols such as bisphenol F, or polyfunctional phenol compounds such as phenol novolac and phenol aralkyl resins. Among these, aralkyl type phenol resins are preferable from the viewpoint of heat resistance and solubility.

  Known epoxy compounds can be used as the epoxy compound, and the epoxy compound is selected from those having two or more epoxy groups in one molecule. Although not particularly limited, for example, bisphenol A, bisphenol F, 3,3 ′, 5,5′-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2′-biphenol, 3,3 ′, 5,5 Epoxidized products of divalent phenols such as' -tetramethyl-4,4'-dihydroxybiphenol, resorcin, naphthalenediols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4 -Hydroxyphenyl) ethane, tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, phenol novolac, o-cresol novolak, etc. The above epoxidized products of phenols, epoxidized products of co-condensation resins of dicyclopentadiene and phenols, epoxidized products of phenol aralkyl resins synthesized from phenols and paraxylylene dichloride, etc., phenols and bischloromethylbiphenyl, etc. And an epoxidized product of a biphenyl aralkyl type phenol resin synthesized from the above, an epoxidized product of a naphthol aralkyl resin synthesized from naphthols and paraxylylene dichloride, and the like. These epoxy resins may be used alone or in combination of two or more. From the viewpoint of heat resistance and solubility, an epoxy resin that is solid at room temperature such as an epoxy resin obtained from phenol aralkyl resins or biphenyl aralkyl resins is preferable.

  The cyanate compound is not particularly limited as long as it is a compound having two or more cyanate groups in one molecule, and known compounds can be used. In the present embodiment, as a preferred cyanate compound, one having a structure in which a hydroxyl group of a compound having two or more hydroxyl groups in one molecule is substituted with a cyanate group can be mentioned. Further, the cyanate compound preferably has an aromatic group, and a cyanate compound having a structure in which the cyanate group is directly connected to the aromatic group can be suitably used. Such a cyanate compound is not particularly limited. For example, bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethylbisphenol F, bisphenol. A novolak resin, brominated bisphenol A, brominated phenol novolak resin, trifunctional phenol, tetrafunctional phenol, naphthalene type phenol, biphenyl type phenol, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, fat The thing of the structure which substituted the hydroxyl groups, such as cyclic phenol and phosphorus containing phenol, by the cyanate group is mentioned. These cyanate compounds may be used alone or in combination of two or more. Further, the cyanate compound described above may be in any form of a monomer, an oligomer and a resin.

  The amino compound is not particularly limited, and examples thereof include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis ( 3-aminophenoxy) benzene, 1, -Bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-Aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] Ether, bis [4- (3-aminophenoxy) phenyl] ether, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene, O-tolidine, m-tolidine, 4,4'-diaminobenzanilide, 2,2'-bi (Trifluoromethyl) -4,4'-diaminobiphenyl, 4-aminophenyl-4-amino benzoate, 2- (4-aminophenyl) -6-amino-benzoxazole and the like. Furthermore, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Sulfone, 3,3′-diaminodiphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-Aminophenoxy) phenyl] propane, 4,4′-bis (4-aminopheno) A) Aromatic amines such as biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether Diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1]. ] Alicyclic amines such as heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-bisaminomethylcyclohexane, isophoronediamine , Ethylenediamine, hexamethylenediamine Octamethylene diamine, decamethylene diamine, diethylene triamine, aliphatic amines such as triethylenetetramine, and the like.

  Although it does not specifically limit as said benzoxazine compound, For example, Fd obtained from Pd type benzoxazine obtained from bifunctional diamines and monofunctional phenols, monofunctional diamines, and bifunctional phenols. Examples include a-type benzoxazine.

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

  Specific examples of the guanamine compound are not particularly limited. For example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine , Tetraacyloxyguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof.

  Specific examples of the glycoluril compound are not particularly limited. For example, 1 to 4 methylol groups of tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, tetramethylolglycoluril are methoxymethylated. Examples thereof include a compound or a mixture thereof, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated, or a mixture thereof.

  Specific examples of the urea compound include, but are not particularly limited to, for example, tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, tetramethoxyethyl urea Etc.

  Moreover, in this embodiment, you may use the crosslinking agent which has an at least 1 allyl group from a viewpoint of a crosslinking property improvement. Specific examples of the crosslinking agent having at least one allyl group include, for example, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2 , 2-bis (3-allyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-) Allylphenols such as hydroxyphenyl) ether, 2,2-bis (3-allyl-4-cyanatophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-cyanatophenyl) propane, bis (3-allyl-4-cyanatosiphenyl) sulfone, bis (3-allyl-4-cyanatophenyl) sulfide, bi (3-allyl-4-cyanatophenyl) ether and other allyl cyanates, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol allyl ether, etc. However, it is not limited to those exemplified. These may be used alone or as a mixture of two or more. Among these, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-hydroxyphenyl) ) Allylphenols such as propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) ether are preferred. .

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

[Crosslinking accelerator]
In the composition for forming a lower layer film for lithography of the present embodiment, a crosslinking accelerator for accelerating the crosslinking and curing reaction can be used as necessary.

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

  Examples of the crosslinking accelerator include, but are not limited to, for example, 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino). Tertiary amines such as methyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5- Imidazoles such as triphenylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra Tetraphenyl such as phenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, tetrasubstituted phosphonium / tetrasubstituted borate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. Examples thereof include boron salts.

  The content of the crosslinking accelerator is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass when the total mass of the composition is usually 100 parts by mass. It is 0.1-5 mass parts from a viewpoint of easiness and economical efficiency, More preferably, it is 0.1-3 mass parts.

[Radical polymerization initiator]
In the composition for forming a lower layer film for lithography of the present embodiment, a radical polymerization initiator can be blended as necessary. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization with light or a thermal polymerization initiator that initiates radical polymerization with heat. The radical polymerization initiator can be, for example, at least one selected from the group consisting of ketone photopolymerization initiators, organic peroxide polymerization initiators, and azo polymerization initiators.

  Such radical polymerization initiator is not particularly limited, and those conventionally used can be appropriately employed. For example, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methylpropan-1-one, 2 , 4,6-trimethylbenzoyl-diphenyl-phosphine oxide, ketone photopolymerization initiators such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide Oxide, methyl acetoacetate Oxide, acetyl acetate peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis ( t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1 , 1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) butane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p -Mentane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutylhydride Peroxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2 , 5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, Isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n -Propylpa Oxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3- Methoxybutyl peroxydicarbonate, di-s-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, kumi Luperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-Butylperoxyneodeca Ate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2- Ethyl hexanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisobutyrate, t-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethylhexanoate, t -Butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t- Butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butyl peroxy-m-toluyl benzoate, t-butyl peroxybenzoate, bis (t-butylperoxy) isophthalate, 2,5- Dimethyl-2,5-bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, Organic peroxide polymerization initiators such as t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,3-dimethyl-2,3-diphenylbutane Is mentioned.

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

  The content of the radical polymerization initiator may be a stoichiometrically required amount, but when the total mass of the composition containing the above-described compound or resin (component (A)) is 100 parts by mass. It is preferable that it is 0.05-25 mass parts, and it is more preferable that it is 0.1-10 mass parts. When the content of the radical polymerization initiator is 0.05 parts by mass or more, there is a tendency that curing can be prevented from being insufficient. On the other hand, the content of the radical polymerization initiator is 25 parts by mass or less. In such a case, the long-term storage stability at room temperature of the composition for forming a lower layer film for lithography tends to be prevented from being impaired.

[Acid generator]
The composition for forming a lower layer film for lithography of the present embodiment may contain an acid generator as necessary from the viewpoint of further promoting a crosslinking reaction by heat. As the acid generator, those that generate an acid by thermal decomposition and those that generate an acid by light irradiation are known, and any of them can be used.

  Although it does not specifically limit as an acid generator, For example, what is described in international publication 2013/024779 can be used. In addition, in this embodiment, an acid generator can be used individually or in combination of 2 or more types.

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

[Basic compounds]
Furthermore, the composition for forming a lower layer film for lithography of the present embodiment may contain a basic compound from the viewpoint of improving storage stability.

  The basic compound serves as a quencher for the acid to prevent the acid generated in a trace amount from the acid generator from causing the crosslinking reaction to proceed. Examples of such basic compounds include primary, secondary or tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, A nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like are exemplified, but not limited thereto.

  Although it does not specifically limit as a basic compound used in this embodiment, For example, the thing as described in international publication 2013/024779 can be used. In addition, in this embodiment, a basic compound can be used individually or in combination of 2 or more types.

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

[Other additives]
In addition, the composition for forming a lower layer film for lithography of the present embodiment may contain other resins and / or compounds for the purpose of imparting thermosetting properties and controlling absorbance. Examples of such other resins and / or compounds include, for example, naphthol resins, xylene resins, naphthol modified resins, phenol modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth) acrylates, dimethacrylates, and trimethacrylates. , Resins containing no heteroaromatic rings such as naphthalene rings such as tetramethacrylate, vinylnaphthalene and polyacenaphthylene, biphenyl rings such as phenanthrenequinone and fluorene, and heteroatoms such as thiophene and indene; Resins, compounds containing alicyclic structures such as cyclodextrin, adamantane (poly) ol, tricyclodecane (poly) ol, and derivatives thereof are exemplified, but are not particularly limited thereto. Furthermore, the composition for forming a lower layer film for lithography of the present embodiment may contain a known additive. Examples of the known additives include, but are not limited to, ultraviolet absorbers, surfactants, colorants, nonionic surfactants, and the like.

[Formation method of lower layer film for lithography]
The formation method of the lower layer film for lithography of the present embodiment includes a step of forming the lower layer film on the substrate using the composition for forming the lower layer film for lithography of the present embodiment.

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

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

  If the lower layer film for lithography of this embodiment is formed from the composition for lower layer film formation for lithography of this embodiment, the formation method will not be specifically limited, A well-known method is applicable. For example, by applying the composition for forming a lower layer film for lithography of the present embodiment on a substrate by a known coating method such as spin coating or screen printing or a printing method, the organic solvent is volatilized and removed. A lower layer film can be formed.

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

  After the formation of the lower layer film, in the case of a two-layer process, a silicon-containing resist layer thereon or a single-layer resist made of ordinary hydrocarbons, in the case of a three-layer process, a silicon-containing intermediate layer is further formed thereon It is preferable to produce a single-layer resist layer that does not contain silicon. In this case, a well-known thing can be used as a photoresist material for forming this resist layer.

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

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

  A polysilsesquioxane-based intermediate layer is preferably used as the silicon-containing intermediate layer for the three-layer process. By giving the intermediate layer an effect as an antireflection film, reflection tends to be effectively suppressed. For example, in a 193 nm exposure process, if a material containing many aromatic groups and high substrate etching resistance is used as the lower layer film, the k value increases and the substrate reflection tends to increase, but the reflection is suppressed in the intermediate layer. Thus, the substrate reflection can be reduced to 0.5% or less. The intermediate layer having such an antireflection effect is not limited to the following, but for 193 nm exposure, a polysilsesquioxy crosslinked with an acid or heat into which a light absorbing group having a phenyl group or a silicon-silicon bond is introduced. Sun is preferably used.

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

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

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

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

  The resist pattern formed by the above method is one in which pattern collapse is suppressed by the lower layer film in the present embodiment. Therefore, by using the lower layer film in the present embodiment, a finer pattern can be obtained, and the exposure amount necessary for obtaining the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used as the etching of the lower layer film in the two-layer process. As gas etching, etching using oxygen gas is suitable. In addition to oxygen gas, an inert gas such as He or Ar, or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO _{2 or} H ₂ gas may be added. Further, gas etching can be performed only with CO, CO ₂ , NH ₃ , N ₂ , NO _{2, and} H ₂ gas without using oxygen gas. In particular, the latter gas is preferably used for side wall protection for preventing undercut of the pattern side wall.

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

  Here, when an inorganic hard mask intermediate film is formed as an intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) is formed by a CVD method, an atomic layer deposition (ALD) method, or the like. The The method for forming the nitride film is not limited to the following, but for example, a method described in Japanese Patent Application Laid-Open No. 2002-334869 (Patent Document 4) and International Publication No. 2004/066377 (Patent Document 5) may be used. it can. A photoresist film can be formed directly on such an intermediate film, but an organic antireflection film (BARC) is formed on the intermediate film by spin coating, and a photoresist film is formed thereon. May be.

  As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. By providing the resist intermediate layer film with an effect as an antireflection film, reflection tends to be effectively suppressed. The specific material of the polysilsesquioxane-based intermediate layer is not limited to the following, but for example, JP 2007-226170 A (Patent Document 6), JP 2007-226204 A (Patent Document 7). Can be used.

Etching of the next substrate can also be performed by a conventional method. For example, if the substrate is SiO ₂ or SiN, etching mainly using a chlorofluorocarbon gas, if p-Si, Al, or W is chlorine or bromine, Etching mainly with gas can be performed. When the substrate is etched with a chlorofluorocarbon gas, the silicon-containing resist of the two-layer resist process and the silicon-containing intermediate layer of the three-layer process are peeled off simultaneously with the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled, and generally, dry etching peeling with a chlorofluorocarbon-based gas is performed after the substrate is processed. .

The lower layer film in this embodiment is characterized by excellent etching resistance of these substrates. The substrate may be appropriately selected and used those known, but are not limited to, include _{Si, α-Si, p-} Si, SiO 2, SiN, SiON, W, TiN, Al and the like . The substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). Such film to be _{processed, Si, SiO 2, SiON,} SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si , etc. Various Low-k film and stopper film In general, a material different from the base material (support) is used. The thickness of the substrate to be processed or the film to be processed is not particularly limited, but is usually preferably about 50 to 1,000,000 nm, more preferably 75 to 500,000 nm.

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

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

  The film forming composition for lithography and the composition for resist permanent film can be prepared by blending the above components and mixing them using a stirrer or the like. Further, when the resist underlayer film composition or resist permanent film composition contains a filler or a pigment, it is adjusted by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill. I can do it.

[Method of purifying compound and / or resin]
The method of purifying the compound and / or resin of the present embodiment includes a step of dissolving the compound of the present embodiment and / or the resin of the present embodiment in a solvent to obtain a solution (S), and the obtained solution (S). A solvent used in the step of obtaining the solution (S) is an organic solvent that is not miscible with water. including.

  In the first extraction step, the resin is preferably a resin obtained by a reaction between the compound represented by the formula (A) and a compound having a crosslinking reactivity. According to the purification method of the present embodiment, the content of various metals that can be contained as impurities in the compound or resin having the specific structure described above can be reduced.

  More specifically, in the purification method of the present embodiment, the compound and / or the resin is dissolved in an organic solvent immiscible with water to obtain a solution (S), and the solution (S) is further converted into an acidic aqueous solution. The extraction process can be carried out in contact with. Thereby, after the metal component contained in the solution (S) containing the compound and / or resin of the present embodiment was transferred to the aqueous phase, the organic phase and the aqueous phase were separated to reduce the metal content. The compound and / or resin of this embodiment can be obtained.

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

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

  Specific examples of the solvent immiscible with water include, but are not limited to, ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate, n-butyl acetate and isoamyl acetate; methyl ethyl ketone, methyl isobutyl ketone, Ketones such as ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone; ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Glycol ether acetates such as n-hexane, n-heptane, etc .; aromatic hydrocarbons such as toluene, xylene; Ren, halogenated hydrocarbons such as chloroform and the like. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferable, More preferred are methyl isobutyl ketone and ethyl acetate. Methyl isobutyl ketone, ethyl acetate, etc. have a relatively high saturation solubility and a relatively low boiling point of the compound and resin of the present embodiment, and therefore the load in the process of removing the solvent industrially or by drying. Can be reduced. These solvents can be used alone or in combination of two or more.

  The acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, and examples thereof include a mineral acid aqueous solution in which an inorganic compound is dissolved in water or an organic acid aqueous solution in which an organic compound is dissolved in water. It is done. Although it does not specifically limit as a mineral acid aqueous solution, For example, the mineral acid aqueous solution which dissolved one or more types of mineral acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, in water is mentioned. Further, the organic acid aqueous solution is not particularly limited. For example, acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluene. An organic acid aqueous solution in which one or more organic acids such as sulfonic acid and trifluoroacetic acid are dissolved in water is exemplified. These acidic aqueous solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid, It is preferably one or more organic acid aqueous solutions selected from the group consisting of tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, An aqueous solution of carboxylic acid such as tartaric acid and citric acid is more preferable, an aqueous solution of sulfuric acid, succinic acid, tartaric acid and citric acid is more preferable, and an aqueous solution of succinic acid is more preferable. Since polyvalent carboxylic acids such as succinic acid, tartaric acid, and citric acid are coordinated to metal ions to produce a chelate effect, it is considered that the metal tends to be removed more effectively. Further, as the water used here, it is preferable to use water having a low metal content, such as ion-exchanged water, in accordance with the purpose of the purification method of the present embodiment.

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

  The amount of acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, but from the viewpoint of reducing the number of extractions for metal removal and securing the operability in consideration of the total liquid amount, It is preferable to adjust the amount used. From the said viewpoint, the usage-amount of acidic aqueous solution becomes like this. Preferably it is 10-200 mass% with respect to 100 mass% of said solutions (S), More preferably, it is 20-100 mass%.

  In the purification method of the present embodiment, the acidic aqueous solution as described above is brought into contact with the solution (S) containing the compound and / or resin of the present embodiment and a solvent immiscible with water. A metal component can be extracted from the compound or the resin in (S).

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

  The organic solvent miscible with water used in the purification method of the present embodiment is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable. Although the usage-amount of the organic solvent mixed with water will not be specifically limited if it is a range which a solution phase and an aqueous phase isolate | separate, It is 0.1-100 mass times with respect to the compound and / or resin of this embodiment. It is preferable that it is 0.1 to 50 times by mass, more preferably 0.1 to 20 times by mass.

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

  The temperature at the time of performing the extraction treatment is usually 20 to 90 ° C, and preferably 30 to 80 ° C. The extraction operation is performed, for example, by mixing the mixture well by stirring or the like and then allowing it to stand. Thereby, the metal content contained in the solution containing the compound and / or resin of the present embodiment and the organic solvent is transferred to the aqueous phase. Moreover, the acidity of a solution falls by this operation and the quality change of the compound and / or resin of this embodiment can be suppressed.

  The mixed solution is allowed to stand to separate into a solution phase containing the compound and / or resin and solvent of the present embodiment and an aqueous phase, so that the compound and / or resin and solvent of the present embodiment are separated by decantation or the like. The containing solution phase is recovered. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation between the solvent-containing solution phase and the aqueous phase. Usually, the time for standing is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times.

  In the purification method of the present embodiment, after the first extraction step, the solution phase containing the compound or the resin is further brought into contact with water to extract impurities in the compound or the resin (second extraction step). ) Is preferably included. Specifically, for example, after performing the above extraction treatment using an acidic aqueous solution, the solution phase containing the compound and / or resin and solvent of the present embodiment extracted and recovered from the aqueous solution is further added with water. It is preferable to use for an extraction process. The extraction treatment with water is not particularly limited. For example, after the solution phase and water are mixed well by stirring or the like, the obtained mixed solution can be left still. Since the mixed solution after standing is separated into a solution phase containing the compound and / or resin and solvent of the present embodiment and an aqueous phase, the compound and / or resin and solvent of the present embodiment by decantation or the like. The solution phase containing can be recovered.

  Moreover, it is preferable that the water used here is water with a low metal content, for example, ion-exchanged water or the like in accordance with the purpose of the present embodiment. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times. Further, the use ratio of both in the extraction process, conditions such as temperature and time are not particularly limited, but they may be the same as those in the contact process with the acidic aqueous solution.

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

  The method for isolating the compound and / or resin of the present embodiment from the obtained solution containing the compound and / or resin of the present embodiment and a solvent is not particularly limited, and removal by reduced pressure, separation by reprecipitation, and It can carry out by well-known methods, such as those combinations. If necessary, known processes such as a concentration operation, a filtration operation, a centrifugal separation operation, and a drying operation can be performed.

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

The evaluation method of the compound is as follows.
<Measurement of thermal decomposition temperature>
Using an EXSTAR6000DSC apparatus manufactured by SII Nanotechnology Inc., about 5 mg of a sample was placed in an aluminum non-sealed container and heated to 500 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen gas (30 ml / min) air stream. At that time, the temperature at which the reduced portion appears in the baseline was defined as the thermal decomposition temperature.

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

<Solubility>
At 23 ° C., the amount of the compound dissolved in propylene glycol monomethyl ether acetate (PGMEA) was evaluated according to the following criteria.
Evaluation A: 30% by mass or more Evaluation C: Less than 30% by mass

(Synthesis Example 1) Synthesis of BisN-1 A container having an internal volume of 100 ml equipped with a stirrer, a cooling pipe, and a burette was prepared. To this container, 1.52 g (9.5 mmol) of 2,7-dihydroxynaphthalene (reagent manufactured by Sigma-Aldrich), 0.9 g (4.7 mmol) of 4-cyclohexylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Company), 1 , 4-dioxane 30 ml, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid was added to prepare a reaction solution. This reaction solution was stirred at 90 ° C. for 3.5 hours to carry out the reaction. Next, the reaction solution is cooled to 40 ° C., 10 ml of hexane is added dropwise and cooled to 10 ° C. to precipitate the reaction product, filtered, washed with hexane, and then subjected to separation and purification by column chromatography. 0.6 g of the target compound (BisN-1) represented by the following formula was obtained.
In addition, the following peaks were found by 400 MHz- ¹ H-NMR, and confirmed to have a chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.2 (2H, OH), 6.8 to 7.8 (14H, Ph-H), 1.4 to 2.7 (11H, cHx-H), 5.3 (1H , C-H)

(Synthesis Example 2) Synthesis of BisN-2 A container having an internal volume of 100 ml equipped with a stirrer, a cooling pipe and a burette was prepared. To this container, 1.52 g (9.5 mmol) of 2,6-dihydroxynaphthalene (Sigma-Aldrich reagent), 0.9 g (4.7 mmol) of 4-cyclohexylbenzaldehyde (Mitsubishi Gas Chemical Co., Ltd.), 1 , 4-dioxane 30 ml, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid was added to prepare a reaction solution. This reaction solution was stirred at 90 ° C. for 3.5 hours to carry out the reaction. Next, the reaction solution is cooled to 40 ° C., 10 ml of hexane is added dropwise and cooled to 10 ° C. to precipitate the reaction product, filtered, washed with hexane, and then subjected to separation and purification by column chromatography. 0.4 g of the target compound (BisN-2) represented by the following formula was obtained.
In addition, the following peaks were found by 400 MHz- ¹ H-NMR, and confirmed to have a chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.2 (2H, OH), 6.7 to 7.8 (14H, Ph-H), 1.4 to 2.7 (11H, cHx-H), 5.3 (1H , C-H)

(Synthesis Example 3) Synthesis of Resin (R1-BisN-1) A four-necked flask having an internal volume of 1 L and equipped with a Dimroth condenser, a thermometer, and a stirring blade and capable of bottoming out was prepared. In this four-necked flask, 33.2 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound (BisN-1) obtained in Synthesis Example 1 in a nitrogen stream, 21.0 g of a 40 mass% formalin aqueous solution (formaldehyde) 280 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.97 mL of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted for 7 hours while refluxing at 100 ° C. under normal pressure. Thereafter, 180.0 g of ortho-xylene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Furthermore, neutralization and water washing were performed, and orthoxylene was distilled off under reduced pressure to obtain 31.7 g of a brown solid resin (R1-BisN-1).

  The obtained resin (R1-BisN-1) was Mn: 1875, Mw: 3610, Mw / Mn: 1.93.

(Synthesis Example 4) Synthesis of Resin (R2-BisN-1) A four-necked flask having an internal volume of 1 L and equipped with a Dimroth condenser, a thermometer, and a stirring blade and capable of bottoming out was prepared. To this four-necked flask, 33.2 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 50.9 g (280 mmol, 4-biphenylaldehyde) of the compound (BisN-1) obtained in Synthesis Example 1 was added in a nitrogen stream. Mitsubishi Gas Chemical Co., Ltd.), Anisole (Kanto Chemical Co., Ltd.) 100 mL, and oxalic acid dihydrate (Kanto Chemical Co., Ltd.) 10 mL were charged and reacted for 7 hours at 100 ° C. under normal pressure. I let you. Thereafter, 180.0 g of ortho-xylene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Furthermore, neutralization and water washing were performed, and 37.5 g of a brown solid resin (R2-BisN-1) was obtained by distilling off the solvent of the organic phase and unreacted 4-biphenylaldehyde under reduced pressure.

  Obtained resin (R2-BisN-1) was Mn: 1610, Mw: 2567, Mw / Mn: 1.59.

[Comparative Example 1]
A four-necked flask with an internal volume of 10 L capable of bottoming was prepared, equipped with a Dimroth condenser, thermometer, and stirring blade. To this four-necked flask, in a nitrogen stream, 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 2.1 kg of 40% by weight formalin aqueous solution (28 mol of formaldehyde, Mitsubishi Gas Chemical Co., Ltd.) )) And 98 mass% sulfuric acid (manufactured by Kanto Chemical Co., Inc.) 0.97 mL were charged and reacted for 7 hours under reflux at 100 ° C. under normal pressure. Thereafter, 1.8 kg of ethylbenzene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Further, neutralization and washing with water were performed, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a light brown solid dimethylnaphthalene formaldehyde resin.

  Subsequently, a four-necked flask having an internal volume of 0.5 L equipped with a Dimroth condenser, a thermometer, and a stirring blade was prepared. This four-necked flask was charged with 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of paratoluenesulfonic acid under a nitrogen stream, and the temperature was raised to 190 ° C. Stir after heating for hours. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was further raised to 220 ° C. to react for 2 hours. After the solvent was diluted, neutralization and water washing were performed, and the solvent was removed under reduced pressure to obtain 126.1 g of a dark brown solid modified resin (CR-1).

[Examples 1-1 to 2-2]
Table 1 shows the results of evaluating the solubility in propylene glycol monomethyl ether acetate (PGMEA) using BisN-1, BisN-2, R1-BisN-1 and R2-BisN-1.

As is clear from Table 1, it was confirmed that the compounds used in Examples 1-1 to 2-2 were excellent in solubility in a solvent.

[Examples 3 to 4, Comparative Example 2]
(Heat resistance and resist performance)
Table 2 shows the results of heat resistance tests and resist performance evaluations using BisN-1, BisN-2, and CR-1.

(Preparation of resist composition)
Using each compound synthesized above, a resist composition was prepared with the formulation shown in Table 2. Of the components of the resist composition in Table 2, the following were used for the acid generator (C), the acid diffusion controller (E), and the solvent.
Acid generator (C)
P-1: Triphenylbenzenesulfonium trifluoromethanesulfonate (Midori Chemical Co., Ltd.)
Acid diffusion controller (E)
Q-1: Trioctylamine (Tokyo Chemical Industry Co., Ltd.)
Solvent S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

(Method for evaluating resist performance of resist composition)
A uniform resist composition was spin-coated on a clean silicon wafer and then pre-exposure bake (PB) in an oven at 110 ° C. to form a resist film having a thickness of 60 nm. The obtained resist film was irradiated with an electron beam with a line and space setting of 1: 1 at 50 nm intervals using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd.). After the irradiation, the resist films were each heated at a predetermined temperature for 90 seconds, and developed by being immersed in a TMAH 2.38 mass% alkali developer for 60 seconds. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a positive resist pattern. About the formed resist pattern, the line and space was observed with the scanning electron microscope (S-4800 by Hitachi High-Technology Co., Ltd.), and the reactivity by the electron beam irradiation of the resist composition was evaluated.

As is clear from Table 2, the compounds used in Example 3 and Example 4 have good heat resistance, but the compound used in Comparative Example 2 was confirmed to be inferior in heat resistance.

  Regarding resist pattern evaluation, in Example 3 and Example 4, a good resist pattern was obtained by irradiation with an electron beam with a line and space setting of 1: 1 at 50 nm intervals. On the other hand, in Comparative Example 2, a good resist pattern could not be obtained.

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

[Examples 5 to 6, Comparative Example 3]
(Preparation of radiation-sensitive composition)
After preparing the components shown in Table 3 to obtain a uniform solution, the obtained uniform solution was filtered through a Teflon (registered trademark) membrane filter having a pore diameter of 0.1 μm to prepare a radiation-sensitive composition. The following evaluation was performed about each prepared radiation sensitive composition.

In addition, the following thing was used as a resist base material in the comparative example 3. FIG.
PHS-1: Polyhydroxystyrene Mw = 8000 (Sigma-Aldrich)
The following were used as the photoactive compound (B).
B-1: Naphthoquinonediazide photosensitizer of chemical structural formula (G) (4NT-300, Toyo Gosei Co., Ltd.)
The following were used as the solvent.
S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

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

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

  When the radiation sensitive compositions in Example 5 and Example 6 were used, a good resist pattern with a resolution of 5 μm could be obtained. Also, the roughness of the pattern was small and good.

  On the other hand, when the radiation sensitive composition in Comparative Example 3 was used, a good resist pattern with a resolution of 5 μm could be obtained. However, the roughness of the pattern was very poor.

  As described above, it was found that in Example 5 and Example 6, it was possible to form a resist pattern having a small roughness and a good shape as compared with Comparative Example 3. As long as the above-described requirements of the present invention are satisfied, radiation-sensitive compositions other than those described in the examples also exhibit the same effect.

  Since the compounds obtained in Synthesis Example 1 and Synthesis Example 2 have a relatively low molecular weight and low viscosity, and the glass transition temperature is as low as 150 ° C. or less, the formation of a lower layer film for lithography using this compound The material can be relatively advantageously enhanced in embedding properties and film surface flatness. In addition, the thermal decomposition temperature is 150 ° C. or higher (Evaluation A), and since it has high heat resistance, it can be used even under high temperature baking conditions.

[Examples 7 to 10, Examples 7A to 10A, Comparative Example 4]
(Preparation of composition for forming underlayer film for lithography)
A composition for forming a lower layer film for lithography was prepared so as to have the composition shown in Table 4. Next, these compositions for forming a lower layer film for lithography were spin-coated on a silicon substrate, and then baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to prepare 200 nm-thick lower layer films. . The following were used about the acid generator, the crosslinking agent, and the organic solvent.
Acid generator: Ditertiary butyl diphenyl iodonium nonafluoromethanesulfonate (DTDPI) manufactured by Midori Chemical Co., Ltd.
Cross-linking agent: Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA)
Novolak: PSM4357 manufactured by Gunei Chemical Co., Ltd.

  Next, an etching test was performed under the following conditions to evaluate etching resistance. The evaluation results are shown in Table 3.

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

(Evaluation of etching resistance)
Etching resistance was evaluated according to the following procedure. First, a novolak underlayer film was prepared under the above conditions except that novolak (PSM4357 manufactured by Gunei Chemical Co., Ltd.) was used. Then, the above-described etching test was performed on this novolac lower layer film, and the etching rate at that time was measured.

  Next, the lower layer films of Examples 7 to 10, Example 7A to 10A, and Comparative Example 4 were prepared under the same conditions as the novolak lower layer film, the etching test was performed in the same manner, and the etching rate at that time was It was measured.

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

  In Examples 7 to 10 and Examples 7A to 10A, it was found that an etching rate superior to that of the novolac lower layer film was exhibited. On the other hand, in the comparative example 4, it turned out that an etching rate is inferior compared with the lower layer film of a novolak.

[Examples 11-14, 11A-14A, Comparative Example 5]
Next, the composition for forming a lower layer film for lithography used in Examples 7 to 10, Examples 7A to 10A and Comparative Example 4 was applied onto a 60 nm line and space SiO ₂ substrate having a film thickness of 80 nm, and 240 ° C. Was then baked for 60 seconds to form a 90 nm lower layer film.

(Evaluation of embeddability)
The embedding property was evaluated by the following procedure. A cross section of the film obtained under the above conditions was cut out and observed with an electron microscope to evaluate the embedding property.

[Evaluation criteria]
A: The lower layer film is embedded in the concavo-convex part of the 60 nm line and space SiO ₂ substrate without defects.
C: There is a defect in the concavo-convex part of the 60 nm line and space SiO ₂ substrate, and the lower layer film is not embedded.

  In Examples 11 to 14 and Examples 11A to 14A, it was found that the embedding property was better than that of the novolac lower layer film.

[Example 15]
Next, the composition for forming a lower layer film for lithography used in Example 7 was applied on a SiO ₂ substrate having a film thickness of 300 nm, and baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds. An underlayer film of 85 nm was formed. On this lower layer film, an ArF resist solution was applied and baked at 130 ° C. for 60 seconds to form a 140 nm-thick photoresist layer.

  As the ArF resist solution, a compound of the following formula (16): 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass are blended. The prepared one was used.

The compound of the following formula (16) was prepared as follows. That is, 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, 0.38 g of azobisisobutyronitrile, The reaction solution was dissolved in 80 mL. This reaction solution was polymerized for 22 hours while maintaining the reaction temperature at 63 ° C. in a nitrogen atmosphere, and then the reaction solution was dropped into 400 mL of n-hexane. The product resin thus obtained was coagulated and purified, and the resulting white powder was filtered and dried overnight at 40 ° C. under reduced pressure to obtain a compound represented by the following formula (16).
(In the formula (16), 40, 40 and 20 indicate the ratio of each structural unit, not a block copolymer.)

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

[Comparative Example 6]
A photoresist layer was directly formed on the SiO ₂ substrate in the same manner as in Example 15 except that the lower layer film was not formed to obtain a positive resist pattern.

[Evaluation]
For each of Example 15 and Comparative Example 6, the shapes of the obtained resist patterns of 45 nm L / S (1: 1) and 80 nm L / S (1: 1) were changed to an electron microscope (S-4800) manufactured by Hitachi, Ltd. Was observed. As for the shape of the resist pattern after development, the resist pattern was not collapsed and the rectangular shape was good, and the resist pattern was evaluated as bad. As a result of the observation, the minimum line width with no pattern collapse and good rectangularity was used as an evaluation index as the resolution. Furthermore, the minimum amount of electron beam energy that can draw a good pattern shape is used as an evaluation index as sensitivity. The results are shown in Table 6.

  As is clear from Table 6, it was confirmed that the lower layer film in Example 15 was significantly superior in both resolution and sensitivity as compared with Comparative Example 6. In addition, it was confirmed that the resist pattern shape after development did not collapse and the rectangularity was good. Furthermore, from the difference in the resist pattern shape after development, it was shown that the lower layer film forming material for lithography in Example 15 had good adhesion to the resist material.

[Example 16]
The composition for forming a lower layer film for lithography used in Example 7 was applied onto a 300 nm thick SiO ₂ substrate and baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds, thereby forming a lower layer having a thickness of 90 nm. A film was formed. On this lower layer film, a silicon-containing intermediate layer material was applied and baked at 200 ° C. for 60 seconds to form an intermediate layer film having a thickness of 35 nm. Further, the ArF resist solution was applied on this intermediate layer film and baked at 130 ° C. for 60 seconds to form a 150 nm-thick photoresist layer. In addition, as a silicon containing intermediate | middle layer material, the silicon atom containing polymer of Unexamined-Japanese-Patent No. 2007-226170 <synthesis example 1> was used.

  Next, the photoresist layer was subjected to mask exposure using an electron beam drawing apparatus (ELIONX Corp .; ELS-7500, 50 keV), baked (PEB) at 115 ° C. for 90 seconds, and 2.38 mass% tetramethylammonium hydroxide. A positive resist pattern of 45 nm L / S (1: 1) was obtained by developing with an aqueous solution of (TMAH) for 60 seconds.

Then, using RIE-10NR manufactured by Samco International, the silicon-containing intermediate layer film (SOG) was dry-etched using the obtained resist pattern as a mask, and then the obtained silicon-containing intermediate layer film pattern was A dry etching process for the lower layer film using the mask and a dry etching process for the SiO ₂ film using the obtained lower layer film pattern as a mask were sequentially performed.

Each etching condition is as shown below.
Etching condition output to resist intermediate layer film of resist pattern : 50W
Pressure: 20Pa
Time: 1 min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 8: 2 (sccm)
Output of etching condition to resist underlayer film of resist intermediate film pattern : 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)
Etching condition output to SiO ₂ film of resist underlayer film pattern : 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: C ₅ F ₁₂ gas flow rate: C ₂ F ₆ gas flow rate: O ₂ gas flow rate
= 50: 4: 3: 1 (sccm)

[Evaluation]
When the pattern cross section (the shape of the SiO ₂ film after etching) of Example 16 obtained as described above was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., the lower layer of the present invention. In the example using the film, the shape of the SiO ₂ film after etching in the multilayer resist processing was rectangular, and it was confirmed that no defects were observed and it was good.

The present invention is a compound that can be used as a component of a photoresist, a resin raw material for a material for electric / electronic parts, a curable resin raw material such as a photo-curable resin, a resin raw material for a structural material, or a resin curing agent. Have industrial applicability.

Claims (30)

A compound represented by the following formula (A).
(In the formula (A), R ^Y is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms,
R ^Z is an m-valent group having 3 to 60 carbon atoms including a cyclic alkyl group having 3 to 30 carbon atoms,
R ^T is each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. An aryl group, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, and a carboxyl group A group, a thiol group, a group in which a hydrogen atom of a hydroxyl group is substituted with an acid dissociable group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group have an ether bond, a ketone bond, or an ester bond. May contain,
Here, at least one of ^RT is a hydroxyl group,
n is each independently an integer of 0 to 8, wherein at least one of n is an integer of 1 to 8,
m is an integer of 1 to 4,
k is each independently an integer of 0-2. ) The compound of Claim 1 whose compound represented by said Formula (A) is a compound represented by following formula (1).
(In the formula (1), R ^Y , R ^Z , m and k have the same meaning as described in the above formula (A).
R ^3A is each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. An aryl group, an optionally substituted alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxyl group, or a thiol group,
R ^4A is each independently a hydrogen atom or an acid dissociable group,
Here, at least one of R ^4A is a hydrogen atom,
m ^6A is each independently an integer of 0 to 7. ) The compound of Claim 2 whose compound represented by said Formula (1) is a compound represented by following formula (1 ').
(In formula (1 ′), R ^Z has the same meaning as described in formula (A).) The compound of Claim 3 whose compound represented by said Formula (1 ') is a compound represented by following formula (2).
The compound of Claim 4 whose compound represented by the said Formula (2) is a compound represented by a following formula (2-1) or a formula (2-2).
  Resin which has the structural unit derived from the compound of any one of Claims 1-5.   The composition containing 1 or more types chosen from the group which consists of the compound of any one of Claims 1-5, and the resin of Claim 6.   The composition for optical component formation containing 1 or more types chosen from the group which consists of the compound of any one of Claims 1-5, and the resin of Claim 6.   A film-forming composition for lithography comprising at least one selected from the group consisting of the compound according to any one of claims 1 to 5 and the resin according to claim 6.   A resist composition containing at least one selected from the group consisting of the compound according to any one of claims 1 to 5 and the resin according to claim 6.   The resist composition according to claim 10, further comprising a solvent. The resist composition according to claim 10 or 11, further comprising an acid generator.   The resist composition according to claim 10, further comprising an acid diffusion controller. A step of forming a resist film on a substrate using the resist composition according to any one of claims 10 to 13,
Exposing at least a portion of the formed resist film;
And developing the exposed resist film to form a resist pattern. A component (A) that is at least one selected from the group consisting of the compound according to any one of claims 1 to 5 and the resin according to claim 6;
A diazonaphthoquinone photoactive compound (B);
A radiation-sensitive composition containing a solvent,
The content of the solvent is 20 to 99% by mass with respect to 100% by mass of the total amount of the radiation-sensitive composition,
The radiation sensitive composition whose content of components other than the said solvent is 1-80 mass% with respect to 100 mass% of the total amount of the said radiation sensitive composition.   Content ratio ((A) / (B) of said component (A), said diazonaphthoquinone photoactive compound (B), and other optional components (D) optionally contained in said radiation sensitive composition ) / (D)) is 1 to 99% by mass / 99 to 1% by mass / 0 to 98% by mass with respect to 100% by mass of the solid content of the radiation-sensitive composition. Radiation sensitive composition.   The radiation-sensitive composition according to claim 15 or 16, wherein an amorphous film can be formed by spin coating.   The manufacturing method of an amorphous film including the process of forming an amorphous film on a board | substrate using the radiation sensitive composition of any one of Claims 15-17. A step of forming a resist film on a substrate using the radiation-sensitive composition according to any one of claims 15 to 17,
Exposing at least a portion of the formed resist film;
A resist pattern forming method including a step of developing the exposed resist film to form a resist pattern.   An underlayer film-forming material for lithography containing at least one selected from the group consisting of the compound according to any one of claims 1 to 5 and the resin according to claim 6. The underlayer film forming material for lithography according to claim 20,
A composition for forming a lower layer film for lithography, comprising a solvent.   The composition for forming a lower layer film for lithography according to claim 21, further comprising an acid generator.   The composition for forming an underlayer film for lithography according to claim 21 or 22, further comprising a crosslinking agent.   The manufacturing method of the lower layer film for lithography including the process of forming a lower layer film on a board | substrate using the composition for lower layer film formation for lithography of any one of Claims 21-23. A step of forming an underlayer film on a substrate using the composition for forming an underlayer film for lithography according to any one of claims 21 to 23;
Forming at least one photoresist layer on the lower layer film;
Irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern. A step of forming an underlayer film on a substrate using the composition for forming an underlayer film for lithography according to any one of claims 21 to 23;
Forming an intermediate layer film on the lower layer film using a resist intermediate layer film material containing silicon atoms;
Forming at least one photoresist layer on the intermediate layer film;
Irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern; and
Etching the intermediate layer film using the resist pattern as a mask to form an intermediate layer film pattern;
Etching the lower layer film using the intermediate layer film pattern as an etching mask to form a lower layer film pattern; and
Etching the substrate using the lower layer film pattern as an etching mask to form a pattern on the substrate. A step of dissolving one or more selected from the group consisting of the compound according to any one of claims 1 to 5 and the resin according to claim 6 in a solvent to obtain a solution (S);
A first extraction step of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the compound and / or the resin,
A purification method, wherein the solvent used in the step of obtaining the solution (S) includes a solvent that is immiscible with water. The acidic aqueous solution is a mineral acid aqueous solution or an organic acid aqueous solution,
The mineral acid aqueous solution is a mineral acid aqueous solution in which at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid is dissolved in water;
The organic acid aqueous solution is a group consisting of acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid. The purification method according to claim 27, which is an organic acid aqueous solution in which at least one selected from the above is dissolved in water.   The solvent immiscible with water is at least one solvent selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethyl acetate. 28. The purification method according to 28. After the first extraction step, the solution phase containing the compound and / or the resin is further brought into contact with water to include a second extraction step of extracting impurities in the compound and / or the resin. 30. The purification method according to any one of 29.