WO2019059202A1 - Semiconductor lithography film forming composition, and resist pattern forming method and device - Google Patents

Abstract

Provided is a semiconductor lithography film forming composition containing a nitryl compound.

Description

Semiconductor lithography film forming composition, and resist pattern forming method and device

The present invention relates to a semiconductor lithography film forming composition, and a method and device for forming a resist pattern.

In the manufacture of semiconductor devices, microfabrication by lithography using a photoresist material is performed, and in recent years, with the high integration and high speed of LSI, further miniaturization by pattern rules is required. In addition, the light source for lithography used at the time of resist pattern formation is shortened in wavelength from KrF excimer laser (248 nm) to ArF excimer laser (193 nm), and the introduction of extreme ultraviolet light (EUV, 13.5 nm) It is also expected.

When the miniaturization of the resist pattern progresses, a problem of resolution or a problem that the resist pattern falls after development occurs, so that thinning of the resist becomes desirable. However, simply reducing the thickness of the resist makes it difficult to obtain a film thickness of a resist pattern sufficient for substrate processing. Therefore, not only a resist pattern, but a resist underlayer film is produced between the resist and the semiconductor substrate to be processed, and a process for providing this resist underlayer film with a function as a mask at the time of substrate processing is also required.

At present, various types of resist underlayer films for such processes are known. For example, unlike a conventional resist underlayer film having a high etching rate, as a material for realizing a resist underlayer film for lithography having a dry etching rate selectivity close to that of a resist, the end groups are removed by application of a predetermined energy. An underlayer film forming material for a multilayer resist process has been proposed which contains a resin component having at least a substituent which generates a sulfonic acid residue and a solvent separately (for example, see Patent Document 1). In addition, a resist underlayer film material containing a polymer having a specific repeating unit has been proposed as a material for realizing a resist underlayer film for lithography having a selection ratio of dry etching rate smaller than that of a resist (for example, patent documents 2). Furthermore, in order to realize a resist underlayer film for lithography having a dry etching rate selectivity smaller than that of a semiconductor substrate, a repeating unit of acenaphthylene is copolymerized with a repeating unit having a substituted or non-substituted hydroxy group. There has been proposed a resist underlayer film material containing a polymer obtained by the above method (see, for example, Patent Document 3).

On the other hand, as a material having high etching resistance in this type of resist underlayer film, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas or the like as a raw material 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.

Moreover, the present inventors are excellent in etching resistance, high heat resistance, and soluble in a solvent, and as a material applicable to a wet process, a lower layer film forming composition for lithography containing a compound of a specific structure and an organic solvent An object (see, for example, Patent Document 4) is proposed.

Furthermore, as a method of forming an intermediate layer used in formation of a resist underlayer film in a three-layer process, for example, a method of forming a silicon nitride film (see, for example, Patent Document 5) and a method of forming a silicon nitride film by CVD (for example, Patent Document 6) is known. Further, as an interlayer material for a three-layer process, a material containing a silsesquioxane-based silicon compound is known (see, for example, Patent Documents 7 and 8).

Various optical component forming compositions have also been proposed, for example, acrylic resins (see, for example, Patent Documents 9 and 10), and / or polyphenols having specific structures derived from allyl groups (see, for example, Patent Document 11) ) Has been proposed.

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

As described above, many film-forming compositions for lithography for resist applications and film-forming compositions for lithography for lower layer films have been proposed, but wet processes such as spin coating and screen printing can be applied. As well as having high solvent solubility, none have achieved both heat resistance and etching resistance at a high level, and development of new materials is required.

Moreover, although many compositions for optical members are proposed conventionally, there is no thing which made heat resistance, transparency, and a refractive index compatible, and development of a new material is called for.

The present invention has been made in view of the problems of the prior art, and a composition for forming a semiconductor lithography film is applicable to form a film which is applicable to a wet process and is excellent in heat resistance, solubility and etching resistance. It aims to provide goods.
Another object of the present invention is to provide a composition that can be used for the production of an optical component having both heat resistance, transparency and refractive index.

As a result of intensive studies to solve the problems of the prior art, the present inventors have found that the problems of the prior art can be solved by a specific semiconductor lithography film forming composition, and complete the present invention. It reached.
That is, the present invention is as follows.

[1]
A semiconductor lithographic film-forming composition comprising a nitrile compound.
[2]
The composition according to [1], wherein the molecular weight of the nitrile compound is in the range of 41 g / mol to less than 1000 g / mol.
[3]
The composition according to [1] or [2], comprising two or more different nitrile compounds.
[4]
The composition as described in [1] or [2] which contains three or more types of different nitrile compounds.
[5]
The composition according to any one of [1] to [4], wherein the nitrile compound is a compound represented by the following formula (1).

(In the above formula (1),
R ^A is an n-valent group having 1 to 70 carbon atoms,
n is an integer of 1 to 10. )
[6]
The composition according to [5], wherein said R ^A is a group containing at least one selected from the group consisting of a linear hydrocarbon group, a branched hydrocarbon group and a ring structure.
[7]
The ring structure described in [6], comprising at least one selected from the group consisting of an aromatic ring which may have a substituent and an alicyclic hydrocarbon group which may have a substituent. Composition of
[8]
The composition according to any one of [1] to [7], wherein the nitrile compound contains an aromatic ring which may have a substituent, and a nitrile group is substituted on the aromatic ring.
[9]
The composition according to any one of [1] to [8], wherein the nitrile compound is a compound represented by the following formula (2).

(In the above formula (2),
X is an aromatic ring which may have a substituent,
Y is a group containing a ring structure,
Z is any one independently selected from the group consisting of a single bond, an ether bond, a thioether bond, a carbonyl bond, an -NH- bond, an amide bond, and an alkylene which may have a substituent,
m1 is an integer of 0 or 1;
n1 is an integer of 1 to 10, and n2 is an integer of 1 or more.
However, the product of n1 and n2 is an integer of 1 to 10. )
[10]
The composition according to any one of [1] to [9], wherein the nitrile compound is a compound represented by the following formula (3) and / or a compound represented by the following formula (4).

(In the above formula (3),
X ^a is an aromatic ring which may have a substituent, and n 1 is an integer of 1 to 10. )

(In the above formula (4),
Each X ^b is independently an aromatic ring which may have a substituent,
Y is a group containing a ring structure,
Z is any one independently selected from the group consisting of a single bond, an ether bond, a thioether bond, a carbonyl bond, an -NH- bond, an amide bond, and an alkylene which may have a substituent,
n1 is each independently an integer of 1 to 10. )
[11]
The composition according to [10], wherein the compound represented by the formula (3) is a compound selected from the following formula (A) group, and the compound represented by the formula (4) is BisAPN or BiFPN object.

[12]
The composition according to any one of [1] to [11], which comprises a nitrile compound having a melting point of 200 ° C. or higher.
[13]
The composition according to any one of [1] to [12], further comprising a solvent.
[14]
The composition according to any one of [1] to [13], further comprising a curing accelerator.
[15]
The composition according to any one of [1] to [14], further comprising a crosslinking agent.
[16]
The composition according to any one of [1] to [15], which is used to form a semiconductor underlayer film.
[17]
The composition according to any one of [1] to [16], which is used for forming an optical component.
[18]
An underlayer film is formed on the substrate using the composition according to any one of [1] to [16],
A method of forming a resist pattern, comprising the steps of forming at least one photoresist layer on the lower layer film, and then irradiating a predetermined region of the photoresist layer with radiation to perform development.
[19]
A device manufactured using the composition according to any one of [1] to [17].

A wet process is applicable to the semiconductor lithographic film forming composition of the present invention, and a film having excellent heat resistance, solubility and etching resistance can be formed. Moreover, the semiconductor lithography film formation composition of this invention can be used for optical component formation, and this optical component is excellent in heat resistance, transparency, and the balance of a refractive index.

Hereinafter, a mode for carrying out the present invention (hereinafter, also referred to as “the present 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.

[Semiconductor lithography film forming composition]
The semiconductor lithographic film formation composition of the present embodiment contains one or more nitrile compounds. The semiconductor lithography film-forming composition according to the present embodiment preferably contains two or more nitrile compounds from the viewpoint of formation of a good film, and three or more nitrile compounds from the viewpoint of retention time of the good film. Is more preferred.
The semiconductor lithography film formation composition of the present embodiment can be a semiconductor lower layer film formation composition, a semiconductor upper layer film formation composition, or an optical component formation composition. That is, this embodiment is also a semiconductor lower layer film forming composition, a semiconductor upper layer film forming composition, or an optical component forming composition, which contains a nitrile compound.

The composition of this embodiment is applicable to a wet process and is useful for forming a photoresist underlayer film excellent in heat resistance and etching resistance.
Further, in the composition of the present embodiment, since the intramolecular crosslinking reaction effectively proceeds at the time of high temperature baking, deterioration of the film is suppressed, and a resist underlayer film excellent in etching resistance to oxygen plasma etching etc. is formed. Can. In addition, since the adhesion with the resist layer is also excellent, an excellent resist pattern can be formed.
Furthermore, since the refractive index is high and the coloring due to a wide range of heat treatment from low temperature to high temperature is suppressed, it is also useful as various optical forming compositions.

The composition for forming a semiconductor lithography film of the present embodiment has a high aromatic density, so that the refractive index is high, and the coloring is suppressed also by a wide range of heat treatment from low temperature to high temperature. It can be used as a composition of
The optical component is not particularly limited, but, for example, a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast improvement lens, etc.) other than film or sheet components Films, films for shielding electromagnetic waves, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, etc. may be mentioned.

The composition of the present embodiment is useful as a film-forming composition for lithography for semiconductor lower layer films (hereinafter, also referred to as "lower layer film-forming material").

The content of the nitrile compound in the composition of the present embodiment is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, when the total amount of the composition is 100% by mass, from the viewpoint of coatability and quality stability. It is 100% by mass, more preferably 50 to 100% by mass, and still more preferably 100% by mass.

The lower layer film forming material of the present embodiment can be applied to a wet process, and is excellent in heat resistance and etching resistance. Furthermore, since the underlayer film forming material of the present embodiment is excellent in intermolecular crosslinking using the above-mentioned substance, degradation of the film at the time of high temperature baking is suppressed, and the underlayer film also excellent in etching resistance to oxygen plasma etching and the like. Can be formed. Furthermore, since the underlayer film forming material of the present embodiment is also excellent in adhesion to the resist layer, an excellent resist pattern can be obtained. In addition, the lower layer film forming material of the present embodiment may include the already known lower layer film forming material for lithography and the like within the range where the effects of the present invention are not impaired.

The nitrile compound in the present embodiment contains at least one cyano group which may be referred to as a nitrile group.
The cyano group in this embodiment can be defined by the formula: -C≡N.
The nitrile compound in the present embodiment may have two or more cyano groups, and the two or more cyano groups are also generally referred to as polycyano groups.
The molecular weight of the nitrile compound in the present embodiment is preferably in the range of 41 g / mol or more and less than 3000 g / mol, more preferably in the range of 41 g / mol or more and less than 1000 g / mol, and 100 g / mol or more and 1000 g / mol. It is more preferable to be in the range of less than 100, and even more preferable to be in the range of 100 g / mol to less than 500 g / mol.

The compound having a polycyano group is represented by the formula: τ- (C≡N) _n [wherein, τ is a polyvalent organic group moiety having a valence of at least 2 and n is a valence of the polyvalent organic group moiety τ Is an integer equal to a number].
τ is a heterocyclic, polyvalent organic moiety. In other words, τ is a heterocyclic group which may be saturated or unsaturated, a heterocyclic group which may be monocyclic, bicyclic, tricyclic or polycyclic, and one or more Or an organic group having a heterocyclic group which may contain the same or different hetero atoms.
τ is preferably an acyclic and multivalent organic group moiety (linear or branched) which may or may not contain one or more hetero atoms.
τ is preferably a cyclic and multivalent organic moiety which does not contain a heteroatom in the ring of the cyclic moiety.
Examples of the hetero atom include nitrogen, oxygen, sulfur, boron, silicon, tin, and phosphorus.

The compound having a polycyano group is preferably represented, for example, by the formula: N≡C—R 1 —C≡N [wherein, R 1 is a divalent organic group].
The divalent organic group is not particularly limited, and examples thereof include a hydrocarbylene group such as an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, an alkynylene group, a cycloalkynylene group, or an arylene group. And substituted hydrocarbylene groups and the like.
A substituted hydrocarbylene group is a hydrocarbylene group in which one or more hydrogen atoms are substituted with a substituent such as an alkyl group.
The divalent organic group may contain from 1 or 2 carbon atoms or a suitable minimum number of carbon atoms forming such a group. These groups may also contain one or more heteroatoms.
R 1 is preferably a non-heterocyclic divalent group.
R 1 is preferably a non-cyclic divalent organic group (linear or branched) which may or may not contain one or more hetero atoms.
R 1 is preferably a cyclic divalent organic group containing no hetero atom.
R1 may contain one or more additional cyano groups (ie, -C≡N).

Examples of the compound having a polycyano group include (polycyano) arene compounds, (polycyano) alkane compounds, (polycyano) alkene compounds, (polycyano) alkyne compounds, (polycyano) cycloalkane compounds, (polycyano) cycloalkene compounds, and Polycyano) cycloalkyne compounds and the like can be mentioned.
Here, the (polycyano) arene compound is a compound in which at least two hydrogen atoms in the arene compound are substituted with a cyano group.

Examples of the (polycyano) arene compound include dicyanoarene compounds, tricyanoarene compounds and tetracyanoarene compounds.
Examples of (polycyano) alkane compounds include dicyanoalkane compounds, tricyanoalkane compounds and tetracyanoalkane compounds.
Examples of (polycyano) alkene compounds include dicyanoalkene compounds, tricyanoalkene compounds and tetracyanoalkene compounds.
Examples of (polycyano) alkyne compounds include dicyanoalkyne compounds, tricyanoalkyne compounds and tetracyanoalkyne compounds.
Examples of (polycyano) cycloalkane compounds include dicyanocycloalkane compounds, tricyanocycloalkane compounds and tetracyanocycloalkane compounds.
Examples of (polycyano) cycloalkene compounds include dicyanocycloalkene compounds, tricyanocycloalkene compounds and tetracyanocycloalkene compounds.
Examples of the (polycyano) cycloalkyne compound include dicyanocycloalkyne compounds, tricyanocycloalkyne compounds, and tetracyanocycloalkyne compounds.

Specific examples of the (polycyano) arene compound include 1,2-dicyanobenzene (phthalonitrile), 1,3-dicyanobenzene (isophthalonitrile or isophthalonitrile), and 1,4-dicyanobenzene (terephthalo). Nitrile), 1,2-dicyanonaphthalene, 1,3-dicyanonaphthalene, 1,4-dicyanonaphthalene, 1,5-dicyanonaphthalene, 1,6-dicyanonaphthalene, 1,7-dicyanonaphthalene, 1,8-dicyano Naphthalene, 2,3-dicyanonaphthalene, 2,4-dicyanonaphthalene, 1,1′-biphenyl) -4,4′-dicarbonitrile, 1,2-dicyanoanthracene, 1,3-dicyanoanthracene, 1,4 -Dicyanoanthracene, 1,8-dicyanoanthracene, 1,9-dicyanoanthrase 2,3-dicyanoanthracene, 2,4-dicyanoanthracene, 9,10-dicyanoanthracene, 9,10-dicyanophenanthrene, 1,2-dicyanoindene, 1,4-dicyanoindene, 2,6-dicyanoindene, 1,2-dicyanoazulene, 1,3-dicyanoazulene, 4,5-dicyanoazulene, 1,8-dicyanofluorene, 1,9-dicyanofluorene, 4,5-dicyanofluorene, 2,6-dicyanotoluene, 2 -Cyanophenylacetonitrile, 4-cyanophenylacetonitrile, 1,3,5-tricyanobenzene, 1,2,4-tricyanobenzene, 1,2,5-tricyanobenzene, 1,4,6-tricyanoindene , 1,3,7-tricyanonaphthalene, 1,2,4,5-tetracyanobenzene and , 3,5,6-tetra-cyano-naphthalene, and the like.

Specific examples of (polycyano) alkane compounds include malononitrile, 1,2-dicyanoethane (succinonitrile), 1,2-dicyano-1,2-diphenylethane, and 1,3-dicyanopropane (glutaronitrile). ), 2-Methylglutaronitrile, 1,2-Dicyanopropane, Dimethylmalononitrile, Diphenylmalononitrile, 1,4-Dicyanobutane (Adiponitrile), 1,5-Dicyanopentane (Pimeronitrile), 1,6-Dicyano Xan (suberonitrile), 1,7-dicyanoheptane, 1,8-dicyanooctane (sebaconitrile), 3,3'-thiodipropionitrile, 1,1,3-tricyanopropane, 1,1,2-tricyano Propane, 1,1,4-tricyanobutane, 1,1,5-tricyanopentane, 1,1,6-tricyanohexane, 1,3,5-tricyanohexane, 1,2,5-tricyanoheptane, 2,4,6-tricyanooctane, tris (2-cyanoethyl) amine, 1,1 And 3,3,4-tetracyanopropane, 1,1,4,4-tetracyanobutane, 1,1,6,6-tetracyanohexane, 1,2,4,5-tetracyanohexane and the like.

Specific examples of (polycyano) alkene compounds include fumaronitrile, 1,3-dicyanopropene, cis-1,4-dicyano-2-butene, trans-1,4-dicyano-2-butene, 2-methylene glycol Tallonitrile, benzylidene malononitrile, 1,1,2-tricyanoethylene, 1,1,3-tricyanopropene, 1,1,4-tricyano-2-butene, 1,1,5-tricyano-2-pentene And tetracyanoethylene, 7,8,8-tetracyanoquinodimethane and 1,1,4,4-tetracyano-2-butene.

Specific examples of (polycyano) alkyne compounds include 3,3-dicyanopropyne, 3,4-dicyano-1-butyne, 3,4-dicyano-1-pentyne and 3,4-dicyano-1-pentyne 3,5-dicyano-1-pentine, 3,4-dicyano-1-hexyne, 3,5-dicyano-1-hexyne, 3,6-dicyano-1-hexyne, 4,5-dicyano-1-hexyne 4,6-dicyano-1-hexyne, 5,6-dicyano-1-hexyne, 1,3,3-tricyanopropyne, 1,3,4-tricyano-1-butyne, 1,3,4- Tricyano-1-pentine, 1,3,4-tricyano-1-pentine, 1,3,5-tricyano-1-pentine, 1,4,5-tricyano-1-pentine, 3,4,5-tricyano- 1-Hexin, 3, 4, 6 Rishiano 1-hexyne, 3,5,6 tricyano-1-hexyne, 3,4,5 tricyano-1-hexyne and 1,1,4,4-tetracyano-2-butyne, and the like.

Specific examples of (polycyano) cycloalkane compounds include 1,2-dicyanocyclobutane, 1,2-dicyanocyclopentane, 1,3-dicyanocyclopentane, 1,2-dicyanocyclohexane, and 1,3-dicyanocyclohexane 1,4-dicyanocyclohexane, 1,2-dicyanocycloheptane, 1,3-dicyanocycloheptane, 1,4-dicyanocycloheptane, 1,2-dicyanocyclooctane, 1,3-dicyanocyclooctane, 1, 4-dicyanocyclooctane, 1,5-dicyanocyclooctane, 1,2,4-tricyanocyclohexane, 1,3,4-tricyanocyclohexane, 1,2,4-tricyanocycloheptane, 1,3,4 -Tricyanocycloheptane, 1,2,4-tricyanocyclooctane, 1, 1,5-tricyanocyclooctane, 1,3,5-tricyanocyclooctane, 1,2,3,4-tetracyanocyclohexane, 2,2,4,4-tetracyclohexane, 1,2,3,4- Tetracyanocycloheptane, 1,1,4,4-tetracyanocycloheptane, 1,2,3,4-tetracyanocyclooctane, 1,2,3,5-tetracyanocyclooctane, 3,3-dimethylcyclo Propane-1,1,2,2-tetracyanocarbonitrile, spiro (2.4) heptane-1,1,2,2-tetracarbonitrile and the like can be mentioned.

Specific examples of the (polycyano) cycloalkene compound include 1,2-dicyanocyclopentene, 1,3-dicyanocyclopentene, 1,4-dicyanocyclopentene, 1,2-dicyanocyclohexene, 1,3-dicyanohexene, 1 , 4-dicyanocyclohexene, 3,6-dicyanocyclohexene, 1,2-dicyanocycloheptene, 1,3-dicyanocycloheptene, 1,4-dicyanocycloheptene, 1,6-dicyanocyclooctene, 3, 4-dicyanocycloheptene, 1,2,3-tricyanocyclopentene, 1,2,4-tricyanocyclopentene, 1,2,4-tricyanocyclohexene, 1,3,5-tricyanocyclohexene, 1,2 , 4-tricyanocycloheptene, 1,3,4-tricyanocycloheptene, 1 2,3-Tricyanocyclooctene, 1,2,5-tricyanocyclooctene, 1,2,3,4-tetracyanocyclohexene, 3,3,4,4-tetracyanocyclohexene, 1,2,4, 5-tetracyanocycloheptene, 3,3,4,4-tetracyanocycloheptene, 1,2,3,4-tetracyanocyclooctene, 3,3,4,4-tetracyanocyclooctene, tricyclo [ 4.2.2.0 (2,5)] deca-3,9-diene-7,7,8,8-tetracarbonitrile, 1,2,6,7-tetracyanocyclooctene, tricyclo [4. 2.2.0 (2,5)] deca-3,9-diene-7,7,8,8-tetracarbonitrile, 3-methyltricyclo [4.2.2.0 (2,5)] Deca-3,9-diene-7,7,8,8-te Lacarbonitrile, 3-phenyltricyclo [4.2.2.0 (2,5)] deca-3,9-diene-7,7,8,8-tetracarbonitrile, 3,4-dimethyltricyclo [4.2.2.0 (2,5)] deca-3,9-diene-7,7,8,8-tetracarbonitrile, bicyclo [7.2.0] undeca-2,4,7- Triene-10,10,11,11-tetracarbonitrile, bicyclo [2.2.1] hept-5-ene-2,2,3,3-tetracarbonitrile and tetracyclo [8.2.2.0 ( 2, 9). 0 (3,8)] tetradeca-3 (8), 13-diene-11, 11, 12, 12-tetracarbonitrile and the like.

Specific examples of the (polycyano) cycloalkyne compound include 1,2-dicyanocyclopentine, 1,3-dicyanocyclopentine, 1,4-dicyanocyclopentine, 1,2-dicyanocyclohexyne, 1 , 3-dicyanohexyne, 1,4-dicyanocyclohexyne, 3,6-dicyanocyclohexyne, 1,2-dicyanocycloheptin, 1,3-dicyanocycloheptene, 1,4-dicyanocycloheptin, 1, 6-dicyanocyclooctin, 3,4-dicyanocycloheptin, 1,2,3-tricyanocyclopentin, 1,2,4-tricyanocyclopentin, 1,2,4-tricyanocyclohexine, 1,3,5-tricyanocyclohexyne, 1,2,4-tricyanocycloheptin, 1,3,4-tricyanocycloheptin, 1 2,3-Tricyanocyclooctin, 1,2,5-Tricyanocyclooctin, 1,2,3,4-Tetracyanocyclohexine, 3,3,4,4-Tetracyanocyclohexine, 1,2, 4,5-tetracyanocycloheptin, 3,3,4,4-tetracyanocycloheptin, 1,2,3,4-tetracyanocyclooctin, 3,3,4,4-tetracyanocyclooctin, Tricyclo [4.2.2.0 (2,5)] deca-3,9-diyne-7,7,8,8-tetracarbonitrile, 1,2,6,7-tetracyanocyclooctin, tricyclo [ 4.2.2.0 (2,5)] deca-3,9-diyne-7,7,8,8-tetracarbonitrile, 3-methyltricyclo [4.2.2.0 (2,5 )] Deca-3,9-Diyne-7,7,8,8-Te Lacarbonitrile, 3-phenyltricyclo [4.2.2.0 (2,5)] deca-3,9-diyne-7,7,8,8-tetracarbonitrile, 3,4-dimethyltricyclo [4.2.2.0 (2,5)] deca-3,9-diyne-7,7,8,8-tetracarbonitrile, bicyclo [7.2.0] undeca-2,4,7- Triin-10,10,11,11-tetracarbonitrile, bicyclo [2.2.1] hept-5-yne-2,2,3,3-tetracarbonitrile and tetracyclo [8.2.2.0 ( 2, 9). 0 (3, 8)] tetradeca-3 (8), 13-diyne-11, 11, 12, 12-tetracarbonitrile etc. are mentioned.

The nitrile compound in the present embodiment is preferably a compound represented by Formula (1). Moreover, it is preferable to contain 1 or more types chosen from the group which consists of a compound represented by Formula (1).

(In the formula (1),
R ^A is an n-valent organic group having 1 to 70 carbon atoms,
n is an integer of 1 to 10. )

R ^A is an n-valent group having 1 to 70 carbon atoms, and a cyano group is bonded via this R ^A.
As said n valent organic group, a linear hydrocarbon group, a branched hydrocarbon group, ring structure etc. are mentioned, for example, The group which these groups were combined may be sufficient. The ring structure preferably contains at least one selected from the group consisting of an aromatic ring which may have a substituent and an alicyclic hydrocarbon group which may have a substituent.
The linear hydrocarbon group and the branched hydrocarbon group may contain an ether bond, a thioether bond, a carbonyl bond, an -NH- bond, an amide bond and the like.

The nitrile compound in the present embodiment is more preferably a compound represented by the following formula (2).

(In the above formula (2),
X is an aromatic ring which may have a substituent,
Y is a group containing a ring structure,
Z is any one independently selected from the group consisting of a single bond, an ether bond, a thioether bond, a carbonyl bond, an -NH- bond, an amide bond, and an alkylene which may have a substituent,
m1 is an integer of 0 or 1;
n1 is an integer of 1 to 10, and n2 is an integer of 1 or more.
However, the product of n1 and n2 is an integer of 1 to 10. )

The nitrile compound in the present embodiment is more preferably a compound represented by the following formula (3) and / or a compound represented by the following formula (4).

(In the above formula (3),
X ^a is an aromatic ring which may have a substituent, and n 1 is an integer of 1 to 10. )

(In the above formula (4),
Each X ^b is independently an aromatic ring which may have a substituent,
Y is a group containing a ring structure,
Z is any one independently selected from the group consisting of a single bond, an ether bond, a thioether bond, a carbonyl bond, an -NH- bond, an amide bond, and an alkylene which may have a substituent,
n1 is each independently an integer of 1 to 10. )

Here, the above-mentioned alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group.
Further, examples of the substituent include linear or branched alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group and butyl group; alkenyl groups such as vinyl group and allyl group; Cyclic hydrocarbon group; crosslinking reactive group; hetero atom; alkoxy group; halogen atom; nitro group; amino group; carboxylic acid group; thiol group; hydroxyl group; and aromatic group having 6 to 60 carbon atoms; And one or more selected from the group consisting of halogenated alkyl groups such as groups;

From the viewpoint of heat resistance and etching resistance, R ^A preferably contains a ring structure.
As a ring structure, an alicyclic hydrocarbon, an aromatic ring, etc. are mentioned, for example.
The alicyclic hydrocarbon in the alicyclic hydrocarbon group is not particularly limited, and examples thereof include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclooctane, cyclodecane, dicyclopentane, tricyclodecane, adamantane, norbornane and the like. It can be mentioned.
The aromatic ring is not particularly limited. For example, benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, naphthacene, chrysene, pyrene, pentacene, benzopyrene, dibenzochrysene, triphenylene, corannulene, coronene, ovalene, fluorene, benzofluorene And acenaphthene.

The group containing a ring structure represented by Y may have a substituent, benzene, diphenyl ether, diphenyl thioether, diphenylmethane, benzophenone, bisphenoxybiphenyl, bicyclohexyl, bicyclohexylmethane, bicyclohexyldimethylmethane, And a group containing at least one selected from the group consisting of a diphenylmethane structure represented by the formula (Y-1) can be mentioned suitably.

In formula (Y-1), R ¹ and R ² each independently represent a linear or branched alkyl group having a carbon number of 1 to 10, such as methyl group, ethyl group, propyl group or butyl group; A linear or branched halogenated alkyl group having 1 to 10 carbon atoms such as a fluoromethyl group;
In addition, R ¹ and R ² may together form a cyclic hydrocarbon and / or aromatic ring structure. The alicyclic hydrocarbon and / or the aromatic ring can be exemplified as described above.

The ring structure is preferably an aromatic ring, and the nitrile group in the nitrile compound is preferably substituted with the above-mentioned aromatic ring, because it is excellent in heat resistance and etching resistance.

Although the specific example of a compound represented by the said Formula (1) is illustrated below, the compound represented by Formula (1) is not limited to the specific example enumerated here.

From the viewpoint of storage stability of the semiconductor lithography film-forming composition, the nitrile compound is preferably a compound selected from the above-mentioned formula (A) group.

From the viewpoint of the high temperature bake resistance of the semiconductor lithography film forming composition, the semiconductor lithography film forming composition preferably contains a nitrile compound having a melting point of 200 ° C. or more.

A commercial item may be used for the nitrile compound in this embodiment, and the compound synthesize | combined using the organic synthesis method may be used.

[solvent]
The semiconductor lithographic film formation composition of the present embodiment may contain a solvent. As a solvent used for a semiconductor lithography film formation composition, if it is a thing which melt | dissolves a nitrile compound at least, a well-known thing can be used suitably.

The solvent is not particularly limited. For example, 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, methyl acetate, ethyl acetate Ester solvents such as butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol and 1-ethoxy-2-propanol; toluene, xylene, anisole, etc. Aromatic hydrocarbons and the like. These solvents can be used alone or in combination of two or more.

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

The content of the solvent is not particularly limited, but is preferably 100 to 10,000 parts by mass, and more preferably 200 to 5,000 parts by mass with respect to 100 parts by mass of the nitrile compound from the viewpoint of solubility of the compound and film formation. More preferably, it is in parts by mass, and more preferably 200 to 1,000 parts by mass.

[Crosslinking agent]
The semiconductor lithographic film formation composition of the present embodiment may contain a crosslinking agent as necessary, from the viewpoint of suppressing intermixing and the like. The crosslinking agent is not particularly limited, and for example, those described in WO 2013/024779 can be used.

The crosslinking agent that can be used in the present embodiment is not particularly limited. For example, phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds And isocyanate compounds and azide compounds. These crosslinking agents can be used singly or in combination of two or more. Among these, benzoxazine compounds, epoxy compounds and cyanate compounds are preferable, and from the viewpoint of improving etching resistance, benzoxazine compounds are more preferable.

As the phenol compound, known compounds can be used. For example, in addition to phenol, cresols, alkylphenols such as xylenols, polyhydric phenols such as hydroquinone, and the like, polycyclic phenols such as naphthols and naphthalenediols, Examples thereof include bisphenols such as bisphenol A and bisphenol F, and polyfunctional phenol compounds such as phenol novolac and phenol aralkyl resin. Among them, aralkyl type phenolic resins are preferable from the viewpoint of heat resistance and solubility.

A well-known thing can be used as said epoxy compound, It selects from the compound which has an epoxy group two or more in 1 molecule. As an epoxy compound, for example, bisphenol A, bisphenol F, 3,3 ', 5,5'-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2'-biphenol, 3,3', 5,5 Epoxides of dihydric phenols such as' -tetramethyl-4,4'-dihydroxybiphenol, resorcine, naphthalenediols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4) -Hydroxyphenyl) ethane, tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylol ethane triglycidyl ether, phenol novolac, o-cresol novolac, etc. Of phenols of higher valency, epoxy compounds of co-condensed resin of dicyclopentadiene and phenols, epoxy compounds of phenol-aralkyl resins synthesized from phenols and paraxylylene dichloride, phenols and bischloromethylbiphenyl The epoxy compound of the biphenylaralkyl type phenol resin synthesize | combined from etc., the epoxy compound of the naphthol aralkyl resin compounds synthesize | combined from naphthols, paraxylylene dichloride etc., etc. are mentioned. These epoxy resins may be used alone or in combination of two or more. From the viewpoint of heat resistance and solubility, solid epoxy resins at room temperature such as epoxy resins obtained from phenol aralkyl resins and biphenyl aralkyl resins are 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. As a cyanate compound in this embodiment, the thing of the structure which substituted the hydroxyl group of the compound which has a 2 or more hydroxyl group in 1 molecule with the cyanate group is mentioned preferably. The cyanate compound is preferably one having an aromatic group, and one having a structure in which the cyanate group is directly linked to the aromatic group can be suitably used. As such a cyanate compound, for example, bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethyl bisphenol F, bisphenol A novolac resin, bromine Bisphenol A, brominated phenol novolac resin, trifunctional phenol, tetrafunctional phenol, naphthalene type phenol, biphenyl type phenol, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, alicyclic phenol, phosphorus The thing of the structure which substituted hydroxyl groups, such as content phenol, to the cyanate group is mentioned. These cyanate compounds may be used alone or in combination of two or more. The above-mentioned cyanate compound may be in the form of any of monomers, oligomers and resins.

Examples of the amino compound 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, 1,3-bis (3-ami Phenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) Phenyl] propane, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4-] (3-Aminophenoxy) phenyl] ether, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9-bis (4-amino-3) -Fluorophenyl) fluorene, O-tolidine, m-tolidine, 4,4'-diaminobenzanilide, 2,2'-bis (trifluoromethane) Le) -4,4'-diaminobiphenyl, 4-aminophenyl-4-amino benzoate, 2- (4-aminophenyl) -6-amino-benzoxazole and the like. Furthermore, as the amino compound, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4 4,4'-Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3 -Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 4,4 -Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] Aromatic amines such as ether, diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) bicyclo [2.2.1] Heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-bisaminomethylcyclohexane, isophorone diamine, etc. Alicyclic amines, ethylene diamide , Hexamethylene diamine, octamethylene diamine, decamethylene diamine, diethylene triamine, aliphatic amines such as triethylenetetramine, and the like.

Examples of the benzoxazine compounds include P-d-type benzoxazines obtained from bifunctional diamines and monofunctional phenols, and Fa-type benzooxazines obtained from monofunctional diamines and difunctional phenols. Can be mentioned.

Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of methoxylmethyl group are methoxymethylated, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, hexame Examples thereof include compounds in which 1 to 6 of the methylol groups of methylolmelamine are acyloxymethylated or a mixture thereof.

Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxyguanamine, tetramethylolamine. Examples thereof include compounds in which 1 to 4 methylol groups of guanamine are acyloxymethylated, or a mixture thereof.

Specific examples of the glycoluril compound include, for example, tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are methoxymethylated, or a mixture thereof. Examples thereof include compounds in which 1 to 4 of methylol groups of tetramethylol glycoluril are acyloxymethylated, a mixture thereof, and the like.

Examples of the urea compound include tetramethylolurea, tetramethoxymethylurea, a compound in which 1 to 4 methylol groups of methoxyethylurea are methoxymethylated or a mixture thereof, and tetramethoxyethylurea.

In addition, in the present embodiment, a crosslinking agent having at least one allyl group may be used from the viewpoint of crosslinkability improvement. The crosslinking agent having at least one allyl group is not particularly limited, and is, for example, 2,2-bis (3-allyl-4-hydroxyphenyl) propane or 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-cyanatophenyl) sulfone, bis (3-allyl-4-cyanatophenyl) sulfide Allyl cyanates such as bis (3-allyl-4-cyanatophenyl) ether, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol allyl ether, etc. . These may be single or a mixture of two or more. Among these, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-hydroxyphenyl) ) Allylphenols such as propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide and bis (3-allyl-4-hydroxyphenyl) ether are preferred .

The content of the crosslinking agent in the semiconductor lithography film-forming composition is not particularly limited, but is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the total mass of the composition. It is a department. By setting the content of the crosslinking agent in the above range, when the film forming composition is used for forming a semiconductor lithography film, the occurrence of mixing phenomenon with the resist layer tends to be suppressed, and the antireflective effect is enhanced. And film formation after crosslinking tends to be enhanced.

[Crosslinking (curing) accelerator]
In the semiconductor lithographic film formation composition of the present embodiment, a crosslinking accelerator (also referred to as a curing accelerator) for accelerating the crosslinking and curing reaction can be used as needed.

The crosslinking accelerator is not particularly limited as long as it promotes crosslinking and curing reaction, and 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) undecen-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, tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, organic phosphines such as diphenyl phosphine and phenyl phosphine, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl Tetra-substituted phosphonium tetra-substituted borate such as tetraphosphorous phosphonium ethyltriphenyl borate and tetrabutyl phosphonium tetra-butyl borate tetraphenyl such as 2-ethyl-4-methylimidazole tetraphenyl borate and N-methyl morpholine tetraphenyl borate Boron salt etc. are mentioned.

The content of the crosslinking accelerator is usually 0.1 to 10 parts by mass when the total mass of the composition is 100 parts by mass, and is more preferably from the viewpoint of controllability and economy. Is 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

[Radical polymerization initiator]
A radical polymerization initiator can be added to the semiconductor lithography film forming composition of the present embodiment as required. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or may be a thermal polymerization initiator that initiates radical polymerization by heat. The radical polymerization initiator 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 a radical polymerization initiator is not particularly limited, and those conventionally used can be appropriately adopted. As a radical polymerization initiator, 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-methyl Ketone-based photopolymerization initiators such as propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methyl ethyl ketone peroxide, Cyclohexanone peroxide, methylcyclohexanone peroxyl Methylacetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1 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-butylperoxy) Cyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, 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) ) Hexin-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoylperoxide O Side, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylper Oxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-s-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α′-bis (neodeca) Noylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t- Hexyl peroxy neodecanoate, -Butylperoxy neodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5- Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t -Butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymaleate, t-butylperoxy-3,5,5- Trimethorhexanoate, t-butyl peroxy laurate, t-butyl peroxyisop Ropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) Isophthalate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t- Organic compounds such as butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 2,3-dimethyl-2,3-diphenylbutane Peroxide type polymerization initiators can be mentioned.

Also, as a radical polymerization initiator, 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-dimethyl valeronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-Methylpropionamidine] dihydridochloride, 2,2'-azobis [N- (4-hydrophenyl) -2-methylpro On amidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydro Chloride, 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane Dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (4,5,6,7-tetrahydro-1H-1) , 3-Diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydrofuran Rimidin-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-methy) Lupropionamide), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl-2,2-azobis (2-methylpropionate) And azo polymerization initiators such as 4,4′-azobis (4-cyanopentanoic acid) and 2,2′-azobis [2- (hydroxymethyl) propionitrile]. As the radical polymerization initiator in the present embodiment, one of these may be used alone, or two or more may be used in combination, and other known polymerization initiators may be further used in combination.

The content of the radical polymerization initiator may be a stoichiometrically necessary amount, but is 0.05 to 25 parts by mass when the total mass of the composition containing the nitrile compound is 100 parts by mass. Is preferably 0.1 to 10 parts by mass. If the content of the radical polymerization initiator is 0.05 parts by mass or more, the curing tends to be insufficient, and 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 underlayer film-forming material tends to be prevented from being impaired.

[Acid generator]
The semiconductor lithographic film formation composition of the present embodiment may contain an acid generator as required, from the viewpoint of further promoting a crosslinking reaction by heat. As an acid generator, although what generate | occur | produces an acid by thermal decomposition, and what generate | occur | produces an acid by light irradiation etc. are known, all can be used. As the acid generator, for example, those described in WO 2013/024779 can be used.

The content of the acid generator in the semiconductor lithography film forming composition is not particularly limited, but is preferably 0.1 to 50 parts by mass when the total mass of the composition containing the nitrile compound is 100 parts by mass, More preferably, it is 0.5 to 40 parts by mass. By setting the content of the acid generator in the above range, the amount of acid generation tends to be large and the crosslinking reaction tends to be enhanced, and the occurrence of mixing phenomenon with the resist layer tends to be suppressed.

[Basic compound]
The semiconductor lithographic film formation composition of the present embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.

The basic compound plays the role of a quencher for the acid to prevent the acid generated in a small amount from the acid generator from proceeding with the crosslinking reaction. Such a basic compound is not particularly limited, and examples thereof include those described in WO 2013/024779.

The content of the basic compound in the semiconductor lithography film-forming composition is not particularly limited, but is preferably 0.001 to 2 parts by mass when the total mass of the composition containing the nitrile compound is 100 parts by mass. More preferably, it is 0.01 to 1 part by mass. By making content of a basic compound into the said range, it exists in the tendency for storage stability to be improved, without impairing crosslinking reaction too much.

[Other additives]
Moreover, the semiconductor lithography film formation composition of this embodiment may contain other resin and / or a compound in order to control hardening property by heat or light, or to control the absorbance. As such other resins and / or compounds, naphthol resin, xylene resin naphthol modified resin, phenol modified resin of naphthalene resin; polyhydroxystyrene, dicyclopentadiene resin, (meth) acrylate, dimethacrylate, trimethacrylate, tetramer Resin containing naphthalene ring such as methacrylate, vinyl naphthalene and polyacenaphthylene, biphenyl ring such as phenanthrene quinone and fluorene, hetero ring having hetero atom such as thiophene and indene, resin not containing aromatic ring; rosin based resin Examples thereof include, but not particularly limited to, resins or compounds containing an alicyclic structure such as cyclodextrin, adamantane (poly) ol, tricyclodecane (poly) ol and derivatives thereof. Furthermore, the underlayer film forming material in the present embodiment may contain known additives. Examples of known additives include, but are not limited to, heat and / or light curing catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photocurable resins, dyes, and pigments. And thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants and the like.

The semiconductor lithographic film formation composition of the present embodiment preferably contains at least a nitrile compound, and further preferably contains a solvent and an acid generator. At this time, when the total of the nitrile compound, the solvent and the acid generator is 100 parts by mass, the composition of the semiconductor lithography film forming composition is 1 to 30 parts by mass of the nitrile compound, 20 to 99 parts by mass of the solvent, and the acid generator The amount is preferably 0.01 to 10 parts by mass, more preferably 1 to 20 parts by mass of nitrile compound, 40 to 99 parts by mass of solvent, 0.01 to 5 parts by mass of acid generator, nitrile compound 1 to 10 More preferably, it is in an amount by mass, 90 to 99 parts by mass of a solvent, and 0.01 to 5 parts by mass of an acid generator.
Moreover, it is preferable that the semiconductor lithography film formation composition of this embodiment contains a solvent, an acid generator, and a crosslinking agent at least further including a nitrile compound. At this time, when the total of the nitrile compound, the solvent, the acid generator and the crosslinking agent is 100 parts by mass, the composition of the semiconductor lithography film forming composition is 1 to 30 parts by mass of the nitrile compound and 20 to 99 parts by mass of the solvent The acid generator is preferably 0.01 to 10 parts by mass, and the crosslinking agent is preferably 0.01 to 10 parts by mass, and the nitrile compound 1 to 20 parts by mass, the solvent 40 to 99 parts by mass, the acid generator 0.01 to 5 parts Part, more preferably 0.1 to 5 parts by mass of a crosslinking agent, 1 to 10 parts by mass of a nitrile compound, 90 to 99 parts by mass of a solvent, 0.01 to 5 parts by mass of an acid generator, 0.5 to 5 parts of a crosslinking agent More preferably, it is 5 parts by mass.

In addition, the semiconductor lithographic film-forming composition of the present embodiment can be produced by blending the polymerizable composition produced by blending with the curing agent in a molten state or the prepolymer in a melted state by heating or the like. The polymerizable composition or prepolymer has an appropriate processing temperature and a wide process temperature, is excellent in curability, and molding and curing can be efficiently performed in the process.

A method of forming a prepolymer or the like in the above process, a method of blending such prepolymer and the like with a filler, processing and curing, and the like to produce a composite can be advanced by a known method.

[Formation method of underlayer film for lithography and multilayer resist pattern]
The underlayer film for lithography in the present embodiment is formed from the above-described semiconductor lithography film forming composition.

In the method for forming a resist pattern according to this embodiment, an underlayer film is formed on a substrate using the above composition, and at least one photoresist layer is formed on the underlayer film, and then the photoresist layer is formed. The process includes irradiating a predetermined area with radiation and performing development. More specifically, in the resist pattern forming method of the present embodiment, a step (A-1) of forming a lower layer film on the substrate using the film forming composition of the present embodiment, and at least one of Forming a photoresist layer of the layer (A-2) and, after the step (A-2), irradiating a predetermined region of the photoresist layer with radiation to perform development (A-3) And.

Furthermore, in the circuit pattern formation method of the present embodiment, an underlayer film is formed on a substrate using the above composition, an interlayer film is formed on the underlayer film using a resist interlayer film material, and the interlayer is formed. Forming at least one photoresist layer on the film;
Irradiating a predetermined area of the photoresist layer with radiation for development to form a resist pattern;
The intermediate layer film is etched using the resist pattern as a mask, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask. Forming a pattern.

More specifically, in the circuit pattern forming method of the present embodiment, a step (B-1) of forming a lower layer film on the substrate using the lower layer film forming material of the present embodiment, and silicon atoms on the lower layer film Forming an intermediate layer film using a resist intermediate layer film material containing B, and forming at least one photoresist layer on the intermediate layer film (B-3); After the step (B-3), a predetermined region of the photoresist layer is irradiated with radiation and developed to form a resist pattern (B-4), and after the step (B-4), The intermediate layer film is etched using the resist pattern as a mask, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask. Having a step (B-5) that forms a pattern.

The lower layer film for lithography in the present embodiment is not particularly limited as long as it is formed of the material for forming a lower layer film of the present embodiment, and known methods can be applied. For example, after the underlayer film material of the present embodiment is applied onto a substrate by a known coating method such as spin coating or screen printing or the like, the organic solvent is removed by volatilization, etc., and then crosslinking is performed by a known method. By curing, the underlayer film for lithography of the present embodiment can be formed. Examples of the crosslinking method include methods such as heat curing and light curing.

At the time of formation of the lower layer film, baking is preferably performed in order to suppress the occurrence of the mixing phenomenon with the upper layer resist and accelerate the crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably 80 to 700 ° C., more preferably 200 to 550 ° C. The baking time is also 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 depending on the required performance, and is not particularly limited, but usually, it is preferably 30 to 20000 nm, more preferably 50 to 15000 nm.

After the underlayer film is formed, in the case of a two-layer process, a silicon-containing resist layer or a single layer resist composed of ordinary hydrocarbons is formed thereon, and in the case of a three-layer process, a silicon-containing intermediate layer is further formed thereon It is preferable to prepare a single layer resist layer not containing silicon. In this case, known photoresist materials can be used as the photoresist material for forming the resist layer.

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

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

As a silicon-containing intermediate layer for the three-layer process, an intermediate layer based on polysilsesquioxane is preferably used. There is a tendency that the reflection can be effectively suppressed by giving the intermediate layer an effect as an antireflective film. For example, in the process for 193 nm exposure, if a material having a large amount of aromatic groups and high substrate etching resistance is used as the lower layer film, the k value tends to be high and the substrate reflection tends to be high. Can make the substrate reflection 0.5% or less. The intermediate layer having such an antireflective effect is not limited to the following, but for exposure at 193 nm, an acid or thermally crosslinked polysilsesqui having a light absorbing group having a phenyl group or a silicon-silicon bond is introduced. Oxane is preferably used.

Further, an intermediate layer formed by a chemical vapor deposition (CVD) method can also be used. For example, a SiON film is known as an intermediate layer produced by a CVD method and having high effect as an antireflective film, although not limited thereto. In general, forming the intermediate layer by a wet process such as spin coating or screen printing rather than the CVD method is simpler and more cost effective. The upper layer resist in the three-layer process may be either positive or negative, and may be the same as a commonly used single layer resist.

Furthermore, the lower layer film in the present embodiment can also be used as a general antireflective film for a single layer resist or a base material for suppressing pattern collapse. The lower layer film is excellent in etching resistance for base processing, so that it can also be expected to function as a hard mask for base processing.

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

The exposure light may be appropriately selected and used according to the photoresist material to be used. In general, high energy rays having a wavelength of 300 nm or less, specifically 248 nm, 193 nm, 157 nm excimer lasers, 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-described method is such that the lower layer film suppresses the pattern collapse. Therefore, by using the lower layer film in the present embodiment, a finer pattern can be obtained, and the amount of exposure required to obtain the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used as the etching of the underlayer film in the two-layer process. As gas etching, etching using oxygen gas is preferable. In addition to oxygen gas, it is also possible to add an inert gas such as He or Ar, or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO _{2 or} H ₂ gas. In addition, gas etching can be performed using only 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 sidewall protection for preventing undercut of the pattern sidewall.

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

Here, when forming an inorganic hard mask intermediate layer film as an intermediate layer, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) are formed by a CVD method, an ALD method, or the like. The method of forming the nitride film is not limited to the following, but, for example, using the method described in Japanese Patent Application Laid-Open No. 2002-334869 (Patent Document 5) and International Publication No. 2004/066377 (Patent Document 6) it can. Although a photoresist film can be formed directly on such an interlayer film, an organic antireflective film (BARC) is formed by spin coating on the interlayer film, and a photoresist film is formed thereon. You may

As the intermediate layer, an intermediate layer based on polysilsesquioxane is also preferably used. There is a tendency that the reflection can be effectively suppressed by giving the resist interlayer film an effect as an antireflective film. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, but, for example, are described in JP-A-2007-226170 (Patent Document 7) and JP-A-2007-226204 (Patent Document 8). Can be used.

In addition, the etching of the next substrate can also be carried out by a conventional method, for example, etching using a fluorocarbon gas as the main component if the substrate is SiO ₂ or SiN, chlorine or bromine if it is p-Si, Al or W Gas-based etching can be performed. When the substrate is etched with a fluorocarbon gas, the silicon-containing resist in the two-layer resist process and the silicon-containing intermediate layer in the three-layer process are peeled off simultaneously with the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled off, and in general, the dry etching peeling by fluorocarbon-based gas is performed after processing the substrate. .

The lower layer film in the present embodiment is characterized in that the etching resistance of the substrate is excellent. In addition, as the substrate, a known substrate can be appropriately selected and used, and although not particularly limited, Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al and the like can be mentioned. Be The substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). As such a film to be processed, various low-k films and stoppers thereof such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc. A film etc. are mentioned, Usually, the material different from a base material (support body) is used. The thickness of the substrate to be processed or the film to be processed is not particularly limited, but it is usually preferably 50 to 10,000 nm, more preferably 75 to 5,000 nm.

The semiconductor lithography film formation composition of this embodiment is used for manufacture of a semiconductor device. That is, one of the present embodiments is a device including the semiconductor lithographic film formation composition of the present embodiment.

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

(Examples 1 to 18, Comparative Example 1)
An underlayer film forming material for lithography having the composition shown in Table 1 was prepared. Next, these underlayer film forming materials for lithography were spin-coated on a silicon substrate, and then baked at 240 ° C. for 60 seconds to form underlayer films each having a film thickness of 200 nm.
The following were used for the compound, the acid generator, the crosslinking agent and the organic solvent.

(Compound)
A-1: benzonitrile (Kanto Chemical Co., melting point: -13 ° C)
A-2: Isophthalonitrile (Kanto Chemical Co., Melting Point: 163-165 ° C.)
BisAPN: compound obtained in Synthesis Example 1 described later BiFPN2: compound obtained in Synthesis Example 2 described later CR-1: resin obtained in Comparative Synthesis Example 1 described later

(Acid generator)
DTDPI: ditertiary butyldiphenyliodonium nonafluoromethanesulfonate (made by Midori Kagaku Co., Ltd.)

(Crosslinking agent)
Sanwa Chemical Corporation Nicarak MX270 (Nicarak)
Konishi Chemical Industries Benzooxazine (BF-BXZ)
Nippon Kayaku Co., Ltd. Biphenyl Aralkyl Type Epoxy Resin (NC-3000-L)
Konishi Chemical Industries, Ltd. diallyl bisphenol A (BPA-CA)
Gunei Chemical Industry Co. diphenylmethane propenyl phenol resin (APG-2)

BF-BXZ;

NC-3000-L;

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

BPA-CA;

APG-2;

(In the above formula, n is an integer of 1 to 3)

(Organic solvent)
Methylene chloride dimethyl sulfoxide (DMSO)
Propylene glycol monomethyl ether acetate (PGMEA)

Synthesis Example 1 Synthesis of Compound (BisAPN) As a raw material, 37.1 g of bisphenol A (reagent made by Kanto Chemical Co., Ltd.) and 200 g of DMF are charged into a 1 L three-necked flask, stirred at room temperature and dissolved to obtain a solution. Obtained. Next, 58.9 g of 4-nitrophthalonitrile (reagent made by Kanto Chemical Co., Ltd.) was added to the above solution, and 50 g of DMF was added, followed by stirring and dissolution. Then, 62.2 g of potassium carbonate and 50 g of DMF were charged together, and the temperature was raised to 85 ° C. with stirring. The reaction was carried out for about 5 hours and cooled at normal temperature. The cooled reaction solution was poured into 0.2 N aqueous hydrochloric acid for neutralization to precipitate a reaction product, and after filtering, the precipitate was washed with water. Then, the filtered reaction product was dried in a vacuum oven at 100 ° C. for 1 day to remove water and residual solvent, and a compound (BisAPN) represented by the following chemical formula was obtained in a yield of 80.3%.

The following peaks were found by 400 MHz- ¹ H-NMR, and it was confirmed that they have the chemical structure of the above formula.
¹ H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.9 to 7.5 (8 H, -O-C ₆ H ₁₀ -O-), 7.8 to 8.1 (6 H, _{-O-C 6 H 3 (CN} ) 2), 1.6 (6H, -C (CH 3) 2)
It was 480 as a result of measuring molecular weight by the said method about the obtained compound.

Synthesis Example 2 Synthesis of Compound (BiFPN) As raw materials, 27.9 g of 4,4′-biphenol (reagent made by Kanto Chemical Co., Ltd.) and 100 mL of DMF were charged into a 1 L three-necked flask and stirred at room temperature for dissolution The solution was obtained. Next, 51.9 g of 4-nitrophthalonitrile (reagent made by Kanto Chemical Co., Ltd.) was added to the above solution, and 50 g of DMF was added, and the mixture was stirred and dissolved. Then, after 62.2 g of potassium carbonate and 50 g of DMF were charged together, the mixture was stirred and the temperature was raised to 85 ° C. After reacting for about 5 hours, the reaction was cooled to normal temperature. The cooled reaction solution was poured into 0.2 N aqueous hydrochloric acid to be neutralized, and the reaction product was precipitated and filtered, and then the precipitate was washed with water. Thereafter, the filtered reaction product was dried in a vacuum oven at 100 ° C. for 1 day. After removing water and residual solvent, a compound (BiFPN) represented by the following chemical formula was obtained in a yield of 83%.

The following peaks were found by 400 MHz- ¹ H-NMR, and it was confirmed that they have the chemical structure of the above formula.
¹ H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.9 to 7.5 (8 H, -O-C ₆ H ₁₀ -O-), 7.8 to 8.1 (6 H, -O-C ₆ H ₃ (CN) ₂ )
It was 438 as a result of measuring molecular weight by the said method about the obtained compound.

(Comparative Example 1)
A four-necked flask with an inner volume of 10 L capable of removing bottom and equipped with a Dimroth condenser, a thermometer and a stirrer was prepared. In this four-necked flask, 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 2.1 kg of a 40% by mass formalin aqueous solution (28 mol as formaldehyde, Mitsubishi Gas Chemical (stock ) And 98 mass% sulfuric acid (Kanto Chemical Co., Ltd. product) were charged and reacted for 7 hours under reflux at 100 ° C. under normal pressure. Thereafter, 1.8 kg of ethylbenzene (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) as a dilution solvent was added to the reaction liquid, 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.
The number average molecular weight (Mn) of the obtained dimethyl naphthalene formaldehyde resin was 562.

Subsequently, a 0.5 L four-necked flask equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. In this four-necked flask, 100 g (0.51 mol) of dimethyl naphthalene formaldehyde resin obtained as described above and 0.05 g of para-toluenesulfonic acid are charged under a nitrogen stream, and the temperature is raised to 190 ° C. 2 After heating for a while, it was stirred. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was raised to 220 ° C. for reaction for 2 hours. The solvent was diluted, neutralized and washed with water, and the solvent was removed under reduced pressure to obtain 126.1 g of a black-brown solid modified resin (CR-1).
The obtained resin (CR-1) had a number average molecular weight (Mn) of 885, a weight average molecular weight (Mw) of 2220, and a Mw / Mn of 4.17.

[Evaluation of etching resistance]
The etching test was performed under the conditions shown below to evaluate the etching resistance. The evaluation results are shown in Table 1.

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

Evaluation of etching resistance was performed in the following procedures.
First, a lower layer film of novolac was produced under the same conditions as in Example 1 except that novolac (PSM 4357 manufactured by Gunei Chemical Co., Ltd.) was used instead of the compound (A-1). Then, the above-mentioned etching test was conducted on the lower layer film of this novolak, and the etching rate at that time was measured.
Next, the above-mentioned etching test was conducted similarly for the lower layer films of Examples 1 to 12 and Comparative Example 1, and the etching rate at that time was measured.
And based on the etching rate of the lower layer film of novolak, etching resistance was evaluated by the following evaluation criteria.

(Evaluation criteria)
A: The etching rate was less than -5% as compared to the novolak underlayer film.
B: The etching rate was higher than −5% and lower than 5% as compared with the underlayer film of novolak.
C: The etching rate exceeded + 5% as compared with the underlayer film of novolak.

(Examples 13 and 14)
Next, each solution of the underlayer film forming material for lithography obtained in Examples 1 and 2 is applied onto a 300 nm thick SiO ₂ substrate and baked at 240 ° C. for 60 seconds to obtain a 70 nm thick film. The lower layer film was formed. A resist solution for ArF was coated on this lower layer film, and baked at 130 ° C. for 60 seconds to form a photoresist layer with a film thickness of 140 nm. In addition, as an ArF resist solution, a compound of the following formula (11): 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass What was prepared was used.

The compound of the formula (11) 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, azobisisobutyronitrile 0.38 g was dissolved in 80 mL of tetrahydrofuran to make a reaction solution. The reaction solution was polymerized under a nitrogen atmosphere at a reaction temperature of 63 ° C. for 22 hours, and then the reaction solution was dropped into 400 mL of n-hexane. The resin thus obtained was coagulated and purified, and the resulting white powder was filtered and dried overnight at 40 ° C. under reduced pressure.

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

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

The shapes and defects of the obtained 55 nm L / S (1: 1) and 80 nm L / S (1: 1) resist patterns were observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd.
The shape of the resist pattern after development was evaluated as “good” with no pattern collapse and good rectangularity, and evaluated as “defect” with the others. Further, as a result of the above observation, the smallest line width free from pattern collapse and having good rectangularity was used as an index of evaluation as “resolution”. Furthermore, the minimum amount of electron beam energy capable of drawing a good pattern shape is used as an index of evaluation as the "sensitivity".
The evaluation results are shown in Table 2.

(Comparative example 2)
A photoresist layer was formed directly on the SiO ₂ substrate in the same manner as in Example 3, except that the lower layer film was not formed, to obtain a positive resist pattern. The results are shown in Table 2.

As is clear from Table 1, in Examples 1 to 12, it was at least confirmed that the etching resistance was better than Comparative Example 1. On the other hand, in Comparative Example 1 using CR-1 (phenol-modified dimethyl naphthalene formaldehyde resin), the etching resistance was poor.
Further, in Examples 13 and 14, it was also confirmed that the resist pattern shape after development was good, and no defect was observed. Furthermore, it was also confirmed that both the resolution and the sensitivity were significantly superior to Comparative Example 2 in which the formation of the lower layer film was omitted.
Furthermore, from the difference in the resist pattern shape after development, it was also confirmed that the underlayer film forming material for lithography used in Examples 1 and 2 had good adhesion to the resist material.

(Examples 15 and 16)
The solution of the underlayer film forming material for lithography prepared in Examples 1 and 2 was coated on a 300 nm thick SiO ₂ substrate and baked at 240 ° C. for 60 seconds to form an underlayer film of 80 nm thickness. . A silicon-containing intermediate layer material was coated on this lower layer film and baked at 200 ° C. for 60 seconds to form an intermediate layer film with a film thickness of 35 nm. Further, the resist solution for ArF was coated on the intermediate layer film and baked at 130 ° C. for 60 seconds to form a photoresist layer having a film thickness of 150 nm. In addition, as a silicon containing intermediate layer material, the silicon atom containing polymer obtained by the following was used.

Dissolve 16.6 g of 3-carboxypropyltrimethoxysilane, 7.9 g of phenyltrimethoxysilane and 14.4 g of 3-hydroxypropyltrimethoxysilane in 200 g of tetrahydrofuran (THF) and 100 g of pure water, and make the liquid temperature 35 ° C. Then, 5 g of oxalic acid was added dropwise, and then the temperature was raised to 80 ° C. to carry out a condensation reaction of silanol. Next, add 200 g of diethyl ether, separate the aqueous layer, wash the organic layer twice with ultra pure water, add 200 g of propylene glycol monomethyl ether acetate (PGMEA), and reduce the pressure while heating the solution temperature to 60 ° C. Below, THF, diethyl ether and water were removed to obtain a silicon atom-containing polymer.

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

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

The respective etching conditions are as shown below.
(Etching conditions of resist pattern to resist interlayer film)
Output: 50W
Pressure: 20 Pa
Time: 1 min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 8: 2 (sccm)
(Etching conditions for resist underlayer film pattern to resist underlayer film)
Output: 50W
Pressure: 20 Pa
Time: 2 min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)
(Etching conditions for resist underlayer film pattern to SiO ₂ film)
Output: 50W
Pressure: 20 Pa
Time: 2 min
Etching gas Ar gas flow rate: C ₅ F ₁₂ gas flow rate: C ₂ F ₆ gas flow rate: O ₂ gas flow rate = 50: 4: 3: 1 (sccm)

[Evaluation]
When the pattern cross section (shape of the SiO ₂ film after etching) obtained as described above was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., the lower layer film of the present embodiment was used. It was confirmed that the shape of the SiO ₂ film after etching in the multi-layered resist processing is rectangular, and no defect is observed in the example.

(Examples 17 to 18)
Using the compounds used in Examples 1 and 2 and Comparative Example 1, optical component forming compositions were prepared with the formulations shown in Table 3 below. Among the components of the optical component forming composition in Table 3, the compounds, the acid generator, the acid crosslinking agent, and the solvent used were those described above.
The optical component-forming composition in a uniform state was spin-coated on a clean silicon wafer and then prebaked (also described as PB) in an oven at 110 ° C. to form an optical component-forming film with a thickness of 1 μm. The prepared optical component forming composition was evaluated as “A” when film formation was good, and “C” when there was a defect in the formed film.

The uniform optical component forming composition was spin coated on a clean silicon wafer and then PB in an oven at 110 ° C. to form a 1 μm thick film. The refractive index (λ = 589.3 nm) at 25 ° C. of the film was measured with a J. A. Woolam multi-incidence spectroscopy ellipsometer VASE. The prepared film was evaluated as "A" when the refractive index is 1.6 or more, "B" when it is 1.55 or more and less than 1.6, and "C" when it is less than 1.55. . Moreover, when transparency ((lambda) = 632.8 nm) is 90% or more, it evaluated as "A" and less than 90% evaluated as "C."

As described above, the present embodiment is not limited to the above embodiment and examples, and modifications can be made as appropriate without departing from the scope of the present invention.

The film formation composition for lithography according to the present invention is applicable to a wet process, and can form a photoresist underlayer film excellent in heat resistance and etching resistance. And this film formation composition for lithography can suppress the deterioration of the film at the time of high temperature baking, and can form the lower layer film excellent also in the etching tolerance to oxygen plasma etching etc. Furthermore, when the lower layer film is formed, the adhesion to the resist layer is also excellent, so that an excellent resist pattern can be formed.

Furthermore, the film-forming composition according to the present invention is useful as various optical component-forming compositions because the refractive index is high and the coloration is suppressed by low-temperature to high-temperature treatment.

Therefore, the present invention includes, for example, insulating materials for electricity, resins for resists, sealing resins for semiconductors, adhesives for printed wiring boards, electrical laminates for electrical equipment, electronic equipment and industrial equipment, etc., electrical equipment , Matrix resin of prepreg mounted on electronic equipment and industrial equipment, buildup laminate material, resin for fiber reinforced plastic, resin for sealing liquid crystal display panel, paint, various coating agents, adhesive, coating for semiconductor Resin, resin for resist for semiconductor, resin for lower layer film formation, film or sheet, plastic lens (prism lens, lenticular lens, microlens, Fresnel lens, viewing angle control lens, contrast improvement lens, etc.) , Retardation film, film for shielding electromagnetic wave, prism, optical fiber, flexi Solder resist le printed circuit, plating resist, multilayer printed wiring boards interlayer insulating film, the optical component such as a photosensitive optical waveguide, it is widely and effectively available.

This application is based on Japanese Patent Application (Japanese Patent Application No. 2017-178844) filed on September 19, 2017, the contents of which are incorporated herein by reference.

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

Claims (19)

1. A semiconductor lithographic film-forming composition comprising a nitrile compound.
2. The composition according to claim 1, wherein the molecular weight of the nitrile compound is in the range of 41 g / mol or more and less than 1000 g / mol.
3. The composition according to claim 1 or 2, comprising two or more different nitrile compounds.
4. The composition according to claim 1 or 2, comprising three or more different nitrile compounds.
5. The composition according to any one of claims 1 to 4, wherein the nitrile compound is a compound represented by the following formula (1).
   

   

   (In the above formula (1),
   R ^A is an n-valent group having 1 to 70 carbon atoms,
   n is an integer of 1 to 10. )
6. The composition according to claim 5, wherein said R ^A is a group containing at least one selected from the group consisting of a linear hydrocarbon group, a branched hydrocarbon group and a ring structure.
7. The ring structure according to claim 6, wherein the ring structure comprises at least one selected from the group consisting of an aromatic ring which may have a substituent and an alicyclic hydrocarbon group which may have a substituent. Composition of
8. The composition according to any one of claims 1 to 7, wherein the nitrile compound contains an aromatic ring which may have a substituent, and a nitrile group is substituted on the aromatic ring.
9. The composition according to any one of claims 1 to 8, wherein the nitrile compound is a compound represented by the following formula (2).
   

   

   (In the above formula (2),
   X is an aromatic ring which may have a substituent,
   Y is a group containing a ring structure,
   Z is any one independently selected from the group consisting of a single bond, an ether bond, a thioether bond, a carbonyl bond, an -NH- bond, an amide bond, and an alkylene which may have a substituent,
   m1 is an integer of 0 or 1;
   n1 is an integer of 1 to 10, and n2 is an integer of 1 or more.
   However, the product of n1 and n2 is an integer of 1 to 10. )
10. The composition according to any one of claims 1 to 9, wherein the nitrile compound is a compound represented by the following formula (3) and / or a compound represented by the following formula (4).
    

    

    (In the above formula (3),
    X ^a is an aromatic ring which may have a substituent, and n 1 is an integer of 1 to 10. )
    

    

    (In the above formula (4),
    Each X ^b is independently an aromatic ring which may have a substituent,
    Y is a group containing a ring structure,
    Z is any one independently selected from the group consisting of a single bond, an ether bond, a thioether bond, a carbonyl bond, an -NH- bond, an amide bond, and an alkylene which may have a substituent,
    n1 is each independently an integer of 1 to 10. )
11. The composition according to claim 10, wherein the compound represented by the formula (3) is a compound selected from the following formula (A) group, and the compound represented by the formula (4) is BisAPN or BiFPN. object.
    

    

    
12. The composition according to any one of claims 1 to 11, comprising a nitrile compound having a melting point of 200 属 C or higher.
13. The composition according to any one of the preceding claims, further comprising a solvent.
14. The composition according to any one of claims 1 to 13, further comprising a curing accelerator.
15. The composition according to any one of the preceding claims, further comprising a crosslinking agent.
16. The composition according to any one of claims 1 to 15, which is used to form a semiconductor underlayer film.
17. The composition according to any one of claims 1 to 16, which is used for forming an optical component.
18. An underlayer film is formed on a substrate using the composition according to any one of claims 1 to 16,
    A method of forming a resist pattern, comprising the steps of forming at least one photoresist layer on the lower layer film, and then irradiating a predetermined region of the photoresist layer with radiation to perform development.
19. A device manufactured using the composition according to any one of the preceding claims.