KR101811064B1 - Process for forming pattern, process for forming resist lower layer film, composition for forming resist lower layer film and resist lower layer film - Google Patents

Abstract

Provided is a composition for forming a resist lower layer film which can form a resist lower layer film excellent in bending resistance, high in pattern transfer performance, and excellent in etching resistance, and can suppress odor of outgas upon formation of a lower layer film The purpose.
The present invention relates to [A] a composition for forming a resist lower layer film containing a compound having a group represented by the following formula (1). In the formula (1), R is a monovalent organic group having 1 to 30 carbon atoms. However, this organic group does not contain an oxygen atom at the terminal of the adjacent sulfur atom. The compound [A] has at least one ring selected from the group consisting of an aromatic ring and a heteroaromatic ring, and the bond represented by * in the group represented by the formula (1) is bonded directly to these rings or via an oxygen atom .
≪ Formula 1 >

Description

TECHNICAL FIELD [0001] The present invention relates to a pattern forming method, a method for forming a resist underlayer film, a composition for forming a resist underlayer film, and a resist underlayer film,

The present invention relates to a composition for forming a resist lower layer film, a resist lower layer film formed from the composition, and a method for forming the same.

In the manufacture of integrated circuit devices, multilayer resist processes have been used today to achieve higher integration. This step will be briefly described. First, a resist undercoat film is formed by applying a composition for forming a resist lower layer film on a substrate to form a resist film thereon, and then a resist film is formed by a stepper )) Or the like to transfer the mask pattern onto a resist film, and the resist pattern is obtained by developing with a suitable developer. Thereafter, this resist pattern is transferred onto the resist lower layer film by dry etching. Finally, the resist underlayer film pattern is transferred onto the substrate to be processed by dry etching to obtain a substrate having a desired pattern formed thereon.

In the above-described multilayer resist process, since the formation pattern is further miniaturized, the lower layer resist film is required to further improve the pattern transfer performance and the etching resistance. With respect to such a demand, various studies have been made on the structure of the polymer or the like contained in the composition for forming a resist lower layer film and the functional groups contained therein (see Japanese Patent Application Laid-Open No. 2004-177668).

On the other hand, RIE (Reactive Ion Etching) is widely used as the above-mentioned dry etching method in addition to the miniaturization of the formation pattern. Therefore, when etching the substrate to be processed using the resist lower layer film as a mask, And the like. If the resist underlayer film is deformed, the pattern transfer performance with respect to the substrate to be processed is inevitably lowered. On the other hand, it has been reported that the bending resistance is improved by introducing an alkylthienyl group into a polymer forming a resist underlayer film (see Japanese Patent Application Laid-Open No. 2010-107790). However, this technique has a problem that the sulfur component increases in the outgas at the time of formation of the resist lower layer film, and the odor increases.

Japanese Patent Application Laid-Open No. 2004-177668 Japanese Patent Application Laid-Open No. 2010-107790

SUMMARY OF THE INVENTION The present invention has been made in view of these problems, and an object of the present invention is to provide a resist underlayer film having excellent bending resistance, high pattern transfer performance and excellent etching resistance, And to provide a composition for forming a resist lower layer film which can be formed.

In order to solve the above problems,

[A] A composition for forming a resist lower layer film containing a compound having a group represented by the following formula (hereinafter also referred to as "[A] compound").

≪ Formula 1 >

(Wherein R is a monovalent organic group having 1 to 30 carbon atoms, provided that the organic group does not contain an oxygen atom at the terminal of the adjacent sulfur atom and * indicates a bond)

The composition for forming a resist lower layer film of the present invention contains a [A] compound having a group represented by the formula (1) (hereinafter also referred to as an "organic sulfonyl group") to form a resist underlayer film excellent in bending resistance and etching resistance . As a result, the pattern transfer performance with respect to the substrate to be processed can be enhanced. The reason why the composition for forming a resist lower layer film contains the [A] compound having an organic sulfonyl group exhibits the above properties is not necessarily clear, but the presence of the organic sulfonyl group improves the strength of the resist underlayer film against the etching gas .

Further, according to the composition for forming a resist lower layer film, it is possible to suppress odor of the outgas upon formation of the resist lower layer film. This is presumably because the sulfur atom contained in the [A] polymer is included as a sulfonyl group bonded to oxygen atoms, and thus it is difficult to generate a sulfur-containing substance having high volatility.

The compound [A] has at least one ring selected from the group consisting of an aromatic ring and a heteroaromatic ring, and the bond represented by * in the group represented by the formula (1) is bonded directly to these rings or via an oxygen atom . According to the composition for forming a resist lower layer film, since the organic sulfonyl group is bonded at the specific position, the bending resistance and the etching resistance of the resulting resist lower layer film are further improved. The compound [A] having the above structure can be easily synthesized from a phenolic compound widely used as a thermosetting resin or a crosslinking compound.

R in Formula 1 is preferably at least one group selected from the group consisting of an aryl group which may have a substituent and a heteroaryl group which may have a substituent. According to the composition for forming a resist lower layer film, the compound [A] has an organic sulfonyl group containing a group having the specific structure described above, whereby the bending resistance and the etching resistance of the obtained resist lower layer film can be further improved. The compound [A] having the above structure can be easily synthesized using an easily available organic sulfonylating reagent.

The compound [A] preferably has a partial structure represented by the following formula (2).

(2)

(Wherein, Q is an aromatic ring or heteroaromatic ring, R is the same as that in Formula 1, Y is a single bond or an oxygen atom, n0 is an integer of 1 or more, R ¹ is a monovalent organic group, And R < ¹ > may be the same or different from each other when R, Y and R < ¹ > are each a plurality)

According to the composition for forming a resist lower layer film, the compound [A] has a partial structure represented by the above formula (2), whereby the bending resistance and the etching resistance of the resulting resist lower layer film can be further improved.

The [A] compound is preferably a polymer. If the compound [A] is a polymer, the bending resistance and the etching resistance of the obtained resist underlayer film are further improved.

The polymer is preferably at least one resin selected from the group consisting of a novolak resin, a resol resin, a styrene resin, an acenaphthylene resin and a polyarylene resin. When the polymer as the [A] compound is the above-mentioned specific resin, the carbon content can be increased, and the bending resistance and the etching resistance can be further improved.

The [A] compound is also preferably a crosslinking compound. If the compound [A] is a crosslinking compound, a crosslinked resist underlayer film having excellent strength can be formed, and as a result, the bending resistance and the etching resistance of the resist underlayer film can be further improved.

It is preferable that the resist underlayer film forming composition further contains a [B] solvent. The composition for forming a resist lower layer film further contains a [B] solvent, so that workability in forming a resist lower layer film can be improved.

The resist underlayer film of the present invention is formed from the resist underlayer film forming composition. Therefore, the resist underlayer film is excellent in bending resistance and etching resistance, and as a result, pattern transfer performance to the substrate to be processed is also excellent.

The method of forming a resist lower layer film of the present invention

(1) a step of applying a composition for forming a resist lower layer film on the upper side of the processed substrate to form a coated film, and

(2) a step of forming the resist underlayer film by heating the above-mentioned coating film

Respectively.

(1) between the resist lower layer film forming process and (2) the resist film forming process,

(1 ') an intermediate layer forming step of forming an intermediate layer on the upper surface side of the resist lower layer film

Lt; / RTI >

(5) In the pattern formation step, the intermediate layer may be further subjected to dry etching.

According to the method for forming the resist lower layer film, it is possible to form the resist lower layer film which is excellent in bending resistance, etching resistance and pattern transfer performance while suppressing odor of outgas upon forming the lower layer film.

INDUSTRIAL APPLICABILITY As described above, according to the composition for forming a resist lower layer film of the present invention, it is possible to provide a resist underlayer film excellent in bending resistance, high pattern transfer performance and excellent etching resistance, .

Hereinafter, embodiments of the composition for forming a resist lower layer film, the method for forming a resist lower layer film and a resist lower layer film of the present invention will be described in this order.

≪ Composition for forming a resist lower layer film &

The resist underlayer film forming composition may contain other optional components as long as it contains the [A] compound, the [B] solvent as a suitable component, and does not impair the effects of the present invention. Each component will be described below.

<[A] compound>

The [A] compound is a compound having a group represented by the above formula (1). The composition for forming a resist lower layer film contains a [A] compound having an organic sulfonyl group represented by the above formula (1), whereby a resist underlayer film excellent in bending resistance and pattern transfer performance and excellent in etching resistance can be formed. Further, it is possible to reduce the sulfur-containing component in the outgas which is generated at the time of forming the resist lower layer film, and it is possible to suppress odor.

The reason why the resist lower layer film forming composition exhibits the above properties by containing the [A] compound is not necessarily clear, but the presence of the organic sulfonyl group contained in the compound [A] . Further, according to the composition for forming a resist lower layer film, odor of the outgas upon formation of the resist lower layer film can be reduced. It is considered that this is because the [A] polymer is not an organic group having a thiophene skeleton or the like as sulfur, but a sulfur-containing substance is difficult to be produced because a sulfur atom is contained as a sulfonyl group.

In the above formula (1), R is a monovalent organic group having 1 to 30 carbon atoms. However, this organic group does not contain an oxygen atom at the terminal of the adjacent sulfur atom. * Indicates a combined hand.

Examples of the monovalent organic group represented by R include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms A cycloalkenyl group having 8 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, and the like. Some or all of the hydrogen atoms of these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, aralkyl groups and heterocyclic groups may be substituted with substituents. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a heterocyclic group having 3 to 15 carbon atoms, An alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an arylcarboxy group, an aryloxycarbonyl group, an amide group, an alkylamido group and an arylamido group such as a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a hydroxyl group, an amino group, a carboxyl group, .

Examples of the alkyl group having 1 to 30 carbon atoms include methyl, ethyl, straight or branched propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, A decyl group, a hexadecyl group, and an icosyl group.

Examples of the alkenyl group having 2 to 30 carbon atoms include an ethenyl group, a linear or branched propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, A tetradecenyl group, a hexadecenyl group, an icosenyl group, and the like.

Examples of the alkynyl group having 2 to 30 carbon atoms include an ethynyl group, a linear or branched propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecenyl group, A tetradecyl group, a hexadecyl group, an icosinyl group and the like.

Examples of the cycloalkyl group having 3 to 30 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, A polycyclic group such as a monocyclic group, dicyclopentyl group, dicyclohexyl group, norbornyl group, adamantyl group, tricyclodecyl group and tetracyclododecyl group.

Examples of the cycloalkenyl group having 3 to 30 carbon atoms include a cyclopropenyl group such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclodecenyl group, Monocyclic tableware; And polycyclic groups such as a dicyclopentenyl group, a dicyclohexenyl group, a norbornenyl group, a tricyclodecynyl group, and a tetracyclododecanyl group.

Examples of the cycloalkynyl group having 8 to 30 carbon atoms include monocyclic groups such as a cyclooctinyl group, a cyclodecinyl group, and a cyclocyclynyl group; And a polycyclic group such as a tetracyclododecinyl group.

Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, A naphthyl group, an anthryl group, a phenanthryl group and the like.

Examples of the aralkyl group having 7 to 30 carbon atoms include a benzyl group and a phenethyl group.

Examples of the heterocyclic group having 3 to 30 carbon atoms include a furanyl group, a furfuryl group, an isobenzofuranyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, an imidazolyl group, a thiophenyl group, A thiazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzo phosphoryl group, a benzoimidazolyl group, a benzooxazolyl group, a benzothiazolyl group, a benzothiazolyl group, , A heteroaryl group such as a benzoisooxazolyl group or a benzothiazolyl group; A non-aromatic aromatic heterocyclic group such as a tetrahydrofuranyl group, a tetrahydrofurfuryl group, a tetrahydropyranyl group, a pyranylmethyl group, a tetrahydropyranylmethyl group, a tetrahydrothiophenyl group, a pyrrolidinyl group, a piperidinyl group, .

Among these R's, from the viewpoint that the strength of the above-mentioned resist underlayer film against the etching gas is effectively improved, and the bending resistance and the etching resistance of the resulting resist underlayer film are improved, an aryl group having 6 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms and a heterocyclic group having 3 to 30 carbon atoms are preferable, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a heteroaryl group having 3 to 30 carbon atoms, which may have a substituent, In view of ease of synthesis of the compound [A], a phenyl group, a tolyl group, a naphthyl group and a thiophenyl group are more preferable.

Specific examples of the organic sulfonyl group represented by the formula (1) include, for example,

Alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, propylsulfonyl, hexylsulfonyl, octylsulfonyl, decylsulfonyl, hexadecylsulfonyl and icosylsulfonyl groups; An alkenylsulfonyl group such as an ethenylsulfonyl group and a propenylsulfonyl group;

An alkynylsulfonyl group such as an ethynylsulfonyl group and a propynylsulfonyl group;

A cycloalkylsulfonyl group such as a cyclobutylsulfonyl group, a cyclopentylsulfonyl group, a cyclohexylsulfonyl group, a cyclooctylsulfonyl group, a norbornylsulfonyl group and an adamantylsulfonyl group; A cycloalkenylsulfonyl group such as a cyclopentylsulfonyl group, a cyclooctynylsulfonyl group and a norbornenylsulfonyl group; A cycloalkynylsulfonyl group such as a cyclopentylsulfonyl group, a cyclododecylsulfonyl group, and a cyclododecylsulfonyl group; An arylsulfonyl group, an anthrylsulfonyl group, an anthrylsulfonyl group, an anthrylosulfonyl group, an anthrylosulfonyl group, an anthrylosulfonyl group, an anthrylosulfonyl group, an anthrylosulfonyl group, an anthrylosulfonyl group, an anthrylosulfonyl group, An arylsulfonyl group such as a naphthyl group; Aralkylsulfonyl groups such as benzylsulfonyl and phenethylsulfonyl;

An isoindolylsulfonyl group, an imidazolylsulfonyl group, a thiophenylsulfonyl group, a phosphorylsulfonyl group, a pyrazolylsulfonyl group, an imidazolylsulfonyl group, an imidazolylsulfonyl group, a thiophenylsulfonyl group, a phosphorylsulfonyl group, a pyrazolylsulfonyl group, A thiazolylsulfonyl group, a benzofuranylsulfonyl group, a benzothiophenylsulfonyl group, a benzothiophenylsulfonyl group, a benzothiophenylsulfonyl group, a benzothiophenylsulfonyl group, a benzothiophenylsulfonyl group, a benzothiophenylsulfonyl group, a benzothiophenylsulfonyl group, Heteroarylsulfonyl groups such as a phthalylsulfonyl group, a benzimidazolylsulfonyl group, a benzoxazolylsulfonyl group, a benzoisooxazolylsulfonyl group and a benzothiazolylsulfonyl group; A tetrahydrofuranylsulfonyl group, a tetrahydrofuranylsulfonyl group, a tetrahydrofurfurylsulfonyl group, a tetrahydropyranylsulfonyl group, a pyranylmethylsulfonyl group, a tetrahydropyranylmethylsulfonyl group, a tetrahydrothiophenylsulfonyl group, a pyrrolidinylsulfonyl group, And a heteroarylsulfonyl group such as a phenylsulfonyl group and a nonylsulfonyl group.

Of these, an arylsulfonyl group, an alkenylsulfonyl group, and a heteroarylsulfonyl group are preferable, and an arylsulfonyl group and a heteroarylsulfonyl group are more preferable, and a phenylsulfonyl group, a p-tolylsulfonyl group, a naphthylsulfonyl group, More preferred is a thiophenylsulfonyl group.

The number of the organic sulfonyl groups in the [A] compound is not particularly limited, and may be one, or two or more. The lower limit of the amount of the organic sulfonyl group present in the compound [A] is preferably 0.0005 mol / g, more preferably 0.001 mol / g, and more preferably 0.003 mol / g, from the viewpoint of further improving the bending resistance and the etching resistance And particularly preferably 0.005 mol / g. The organic sulfonyl group in the [A] compound may be one kind or plural kinds.

The bonding position of the organic sulfonyl group in the [A] compound is not particularly limited, but from the viewpoint of improving the bending resistance, pattern transfer performance and etching resistance, the compound [A] is selected from the group consisting of aromatic rings and heteroaromatic rings , And it is preferable that the bonding hand represented by * in the group represented by the formula (1) is directly bonded to these rings via an oxygen atom. That is, it is preferable that the [A] compound has a partial structure represented by the general formula (2).

In the above formula (2), Q is an aromatic ring or a hetero aromatic ring. R is synonymous with the above formula (1). Y is a single bond or an oxygen atom. n0 is an integer of 1 or more. R ¹ is a monovalent organic group. m0 is an integer of 0 or more. Provided that when R, Y and R ¹ are each plural, plural R, Y and R ¹ may be the same or different.

The aromatic ring represented by Q may be, for example, a benzene ring. Examples of the heteroaromatic ring represented by Q include a furan ring, a pyrrole ring, a thiophen ring, a phosphole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, a pyridine ring, , Pyrimidine ring, pyridazin ring, triazine ring and the like.

As n0, an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and 1 or 2 is more preferable.

M0 is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and still more preferably an integer of 0 to 2.

Examples of the monovalent organic group represented by R ¹ include monovalent organic groups represented by R in the above formula (1).

The aromatic ring and the heteroaromatic ring in the partial structure represented by the general formula (2) may form a covalent bond with a partial structure other than the partial structure, or may be condensed with a benzene ring or a heteroaromatic ring in another partial structure It is possible.

The compound [A] is preferably a polymer (hereinafter also referred to as &quot; [A1] polymer &quot;). Further, a crosslinkable compound (hereinafter also referred to as &quot; [A2] crosslinkable compound &quot;) is also preferable. Hereinafter, [A1] polymer and [A2] crosslinkable compound will be described in this order.

<[A1] Polymer>

The [A1] polymer is a polymer having a group represented by the above formula (1). When the [A1] polymer has the above organic sulfonyl group, the strength of the obtained resist underlayer film is improved, and as a result, the bending resistance and the etching resistance are further improved.

The polymer [A1] is not particularly limited as long as it is a polymer having an organic sulfonyl group, but a polymer containing an aromatic ring is preferable from the viewpoint that the carbon content can be increased and the bending resistance and the etching resistance are further improved.

Examples of the polymer containing the aromatic ring include novolak resins, resol resins, styrene resins, acenaphthylene resins, polyarylene resins, and the like.

Examples of the novolac resin include phenols such as phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol and p-octylphenol,? -Naphthol,? -Naphthol, Dihydroxynaphthalene, and 2,7-dihydroxynaphthalene, an aldehyde or a divinyl compound, or the like with an acidic catalyst or the like And a resin to be obtained.

Examples of the aldehydes include aldehydes such as formaldehyde; Paraformaldehyde, trioxane, and other aldehyde sources.

Examples of the divinyl compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna- 2-ene,? -Pinene,? -Pinene, limonene, 5-vinylnorbornadiene, and the like.

Examples of the polymer containing the aromatic ring include a polymer having a structural unit represented by the following formula (a).

<Formula a>

In the formula (a), Ar represents (m0 + n0 + p0 + 1) valent aromatic group.

Y ⁰ each independently represents a single bond, an oxygen atom or -NR'-. R 'is a hydrogen atom or a monovalent organic group.

R ¹⁰ is the same as R in the above formula (1).

R ²⁰ each independently represents a group selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, a glycidyl ether group, Lt; / RTI &gt; The alkyl group of the alkyl glycidyl ether group has 1 to 6 carbon atoms. Some or all of the hydrogen atoms of these alkyl groups, alkoxy groups, alkoxycarbonyl groups, aryl groups, glycidyl ether groups and alkyl glycidyl ether groups may be substituted with substituents.

Z ⁰ is a single bond, a methylene group, an alkylene group having 2 to 20 carbon atoms, an arylene group having 6 to 14 carbon atoms, or an oxyalkylene group. Some or all of the hydrogen atoms of these methylene, alkylene, arylene and oxyalkylene groups may be substituted with substituents.

p0 represents a number of bonds in which Z ⁰ is bonded to Ar, and is an integer of 1 to 6; m0 is an integer of 0 to 6; n0 is an integer of 1 to 6; * Indicates a combined hand.

Examples of the aromatic group having at least (m0 + n0 + p0 + 1) valences represented by Ar include a benzene ring aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a phosphorus ring and a fluorenylidenebiphenyl ring, a furan ring, (M0 + n0 + p0 + 1) from a heterocyclic ring such as an oxadiazole ring, an oxazole ring, an oxazole ring, an oxazole ring, a pyrazine ring, ) Hydrogen atoms are removed.

Examples of the polymer having a structural unit represented by the formula (a) include a polymer having a structural unit represented by the following formula (a1) and a structural unit represented by the formula (a2).

<Formula a1>

<Formula a2>

Of the above formulas (a1) and (a2)

Y ¹ and Y ² are each independently a single bond, an oxygen atom or -NR'-. R 'is a hydrogen atom or a monovalent organic group. R &lt; ¹¹ &gt; and R &lt; ¹² &gt; n1 is an integer of 1 to 6; n2 is an integer of 1 to 4; When n1 and n2 are each 2 or more, plural Y ¹ and R ¹¹ and Y ² and R ¹² may be the same or different.

R ²¹ and R ²² each independently represent a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, a glycidyl ether group, Alkyl glycidyl ether group. The alkyl group of the alkyl glycidyl ether group has 1 to 6 carbon atoms. Some or all of the hydrogen atoms of these alkyl groups, alkoxy groups, alkoxycarbonyl groups, aryl groups, glycidyl ether groups and alkyl glycidyl ether groups may be substituted with substituents.

m1 is an integer of 0 to 6; m2 is an integer of 0 to 4; However, it may be the same or different, respectively m1 and m2, if there are more than 2, respectively, a plurality of R ²¹ and R ^22.

Z ¹ and Z ² are a single bond, a methylene group, an alkylene group having 2 to 20 carbon atoms, an arylene group having 6 to 14 carbon atoms, or an oxyalkylene group. Some or all of the hydrogen atoms of these methylene, alkylene, arylene and oxyalkylene groups may be substituted with substituents. p1 represents a number of coupling which Z ¹ is bonded to the aromatic ring and is an integer of 1-6. p2 represents a number of bonds in which Z ² is bonded to an aromatic ring and is an integer of 1 to 4; When p1 and p2 are each 2 or more, plural Z &lt; ^{1 &gt;} and Z &lt; ² &gt; may be the same or different. When p1 and p2 are each 2 or more, Z ¹ and Z ² are bonded to two or more aromatic rings, and the polymer having an aromatic ring has a branched structure or a network structure.

n1, m1 and p1 satisfy 1? n1 + m1 + p1? 7, and n2, m2 and p2 satisfy 1? n2 + m2 + m2? 7. * Indicates a combined hand.

Examples of the monovalent organic group represented by R 'in the -NR'- of Y ¹ and Y ² include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms , An aralkyl group having 7 to 20 carbon atoms, and the like.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ²¹ and R ²² include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2- , t-butyl group and the like.

Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ²¹ and R ²² include a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, , 1-methylpropoxy group, t-butoxy group, 2-propynyloxy group and the like.

Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms represented by R ²¹ and R ²² include a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, Propoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group and the like.

Examples of the aryl group having 6 to 14 carbon atoms represented by R ²¹ and R ²² include a phenyl group and a naphthyl group.

Examples of the alkyl glycidyl ether group represented by R ²¹ and R ²² include a methyl glycidyl ether group, an ethyl glycidyl ether group, a propyl glycidyl ether group, and a butyl glycidyl ether group. .

The alkylene group having 2 to 20 carbon atoms represented by Z ¹ and Z ² includes, for example, an ethylene group; A propylene group such as a 1,3-propylene group and a 1,2-propylene group; Propylene group, a 2-methyl-1,2-propylene group, a 1-methyl-1, 3-propylene group, , 4-butylene group, 2-methyl-1,4-butylene group and the like.

Examples of the arylene group having 6 to 14 carbon atoms represented by Z ¹ and Z ² include a phenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group.

The alkylene chain of the oxyalkylene group represented by Z ¹ and Z ² preferably has 2 to 20 carbon atoms. Examples of such an oxyalkylene group include an oxyethylene group; An oxypropylene group such as a 1,3-oxypropylene group and a 1,2-oxypropylene group; An oxytetramethylene group, an oxypentamethylene group, an oxyhexamethylene group, and the like.

R ²⁰ , R ²¹ , R ²² , Z ⁰ , Z ¹ and Z ² may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, and an aryl group having 6 to 22 carbon atoms. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the alkyl group having 1 to 9 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, . Examples of the aryl group having 6 to 22 carbon atoms include a phenyl group and a naphthyl group.

As the resole resin, for example, a polymer obtained by reacting the phenolic compound with the aldehyde using an alkaline catalyst can be given.

As the styrene resin, for example, a polymer having a structural unit represented by the following formula (a3) may be mentioned.

<Formula a3>

In the formula (a3), Y3 is a single bond, an oxygen atom or -NR'-. R 'is a monovalent organic group. R ¹³ is synonymous with R in the above formula (1). n3 is an integer of 1 to 5; When n3 is 2 or more, a plurality of Y &lt; ³ &gt; And R &lt; ¹³ &gt; may be the same or different.

R ²³ each independently represents an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group. m ³ is an integer of 0 to 4; When m &lt; ³ &gt; is 2 or more, plural R &lt; ²³ &gt; may be the same or different.

n3 and m3 satisfy 1? n3 + m3? 5.

Examples of the monovalent organic group represented by R 'in -NR'- of Y ³ include groups similar to those of R ¹ in Y ^{1 in} the above formula (a2).

Examples of the alkyl group represented by R ²³ include alkyl groups having 1 to 10 carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, , 1-methylpropyl group, t-butyl group and the like.

Examples of the aryl group represented by R ²³ include an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The styrene resin may have another structural unit other than the structural unit represented by the above formula (a3). Further, another structural unit may have the above organic sulfonyl group.

The monomer providing the above other structural unit is not particularly limited, and examples thereof include compounds having various polymerizable unsaturated bonds. (Meth) acrylonitrile, (meth) acrylic acid, (meth) acrylic acid esters such as methyl (meth) acrylate, (meth) acrylic acid esters such as ) Acrylamide; Vinyl ethers such as ethyl vinyl ether, maleic anhydride, vinyl acetate, and vinyl pyridine. Monomers having an organic sulfonyl group bonded thereto are also preferably used.

The content of the other structural units in the styrene resin is preferably less than 50 mol%, more preferably less than 40 mol% based on the total structural units constituting the styrene resin.

The degree of polymerization of the styrene resin, that is, the total number of structural units and other structural units represented by the formula (a3) is preferably 5 or more and 200 or less, more preferably 10 or more and 150 or less.

As the precursor polymer for forming the above styrene resin (particularly polyvinyl phenol-based polymer), commercially available products may be used. For example, "Maruka Linker M" (poly-p-vinylphenol) manufactured by Maruzen Co., Linker MB (brominated poly-p-vinylphenol), Linker CMM (p-vinylphenol / methyl methacrylate copolymer), Linker CHM (p-vinylphenol / methacrylic acid 2-hydroxy Ethyl copolymer), "Linker CST" (p-vinylphenol / styrene copolymer), and the like.

As the acenaphthylene resin, for example, a polymer having a structural unit represented by the following formula (a4) may, for example, be mentioned.

<Formula a4>

In the above formula (a4)

Y ⁴ is a single bond, an oxygen atom or -NR'-. R 'is a monovalent organic group. R ¹⁴ is synonymous with R in the above formula (1). n4 is an integer of 1 to 6; When n4 is 2 or more, a plurality of Y ⁴ and R ¹⁴ may be the same or different.

R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Some or all of the hydrogen atoms of these alkyl groups, alkoxy groups, alkoxycarbonyl groups and aryl groups may be substituted with substituents.

R ²⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Some or all of the hydrogen atoms of these alkyl groups, alkoxy groups, alkoxycarbonyl groups and aryl groups may be substituted with substituents. m4 is an integer of 0 to 5; When m4 is 2 or more, plural R &lt; ²⁶ &gt; may be the same or different.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ²⁴ to R ²⁶ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2- , t-butyl group and the like.

Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ²⁴ to R ²⁶ include a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, , 1-methylpropoxy group, t-butoxy group and the like.

Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms represented by R ²⁴ to R ²⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, Propoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group and the like.

Examples of the aryl group having 6 to 14 carbon atoms represented by R ²⁴ to R ²⁶ include a phenyl group and a naphthyl group.

Examples of the halogen atom represented by R ²⁴ and R ²⁵ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the substituent which R ²⁴ to R ²⁶ may have include a halogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms, and an aryl group having 6 to 22 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group having 1 to 9 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, .

Examples of the aryl group having 6 to 22 carbon atoms include a phenyl group and a naphthyl group.

The above-mentioned acenaphthylene resin can be obtained by polymerizing a compound having an acenaphthylene skeleton with an appropriate polymerization form such as bulk polymerization, solution polymerization, etc. by radical polymerization, anion polymerization, cation polymerization or the like. [0008] Further, as described in paragraphs [0008] to [0031] of Japanese Patent Application Laid-Open No. 2002-296789, paraformaldehyde is reacted with a polymer of a compound having an acenaphthylene skeleton under acidic conditions You can get it.

Examples of the polyarylene resin include polyarylene ether, polyarylene sulfide, polyarylene ether sulfone, and polyarylene ether ketone.

The weight average molecular weight (Mw) of the [A1] polymer in terms of polystyrene is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 1,200 to 40,000.

The polystyrene reduced number average molecular weight (Mn) of the [A1] polymer is preferably 400 to 80,000, more preferably 800 to 40,000, and still more preferably 1,000 to 35,000.

[A1] The ratio of Mw to Mn (Mw / Mn ratio) of the polymer is usually 1 to 5, and more preferably 1 to 3. The values of Mw and Mn can be obtained by measuring monodispersed polystyrene as a standard sample by gel permeation chromatography (GPC).

The resist underlayer film-forming resin composition of the present invention may contain only one kind of the [A1] polymer, or may contain two or more kinds of the [A1] polymers.

<[A2] Crosslinkable compound>

[A2] The crosslinkable compound is a crosslinkable compound having a group represented by the above formula (1). [A2] Since the crosslinkable compound has the above organic sulfonyl group, the strength of the obtained resist lower layer film is improved by the crosslinking reaction, and as a result, the bending resistance and the etching resistance are further improved.

[A2] The crosslinking compound is not particularly limited as long as it has the above organic sulfonyl group and at least one crosslinkable functional group. Means a functional group capable of forming a crosslinking between the crosslinking compound or the crosslinking compound and the other compound by the reaction of the crosslinking functional group or the functional group with the crosslinking functional group do.

Examples of the crosslinkable functional group include a nitrogen atom-containing group such as an amino group in which at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group is bonded; A heterocyclic 3-membered ring such as an epoxy group and a thioepoxy group, and a heterocyclic 4-membered ring containing group; A group having an unsaturated bond such as an isocyanate group, an azide group or an alkenyl ether group; And a hydroxyl group-containing group such as a hydroxyaryl group.

Examples of the crosslinkable compound include a melamine compound in which the methylol group is bonded to a nitrogen atom, a guanamine compound, a glycoluril compound and a urea compound, an epoxy compound, a thioepoxy compound, an isocyanate compound, an azide compound, an alkenyl ether compound, And the like. The crosslinkable compound may be a low molecular weight compound, but it may be one in which a crosslinkable functional group is introduced as a pendant group into the side chain of the polymer.

[A2] Examples of the crosslinkable compound include compounds represented by the following formulas.

In the above formula, R is synonymous with the above formula (1).

The resin composition for forming a resist lower layer film may contain only one kind of [A2] crosslinkable compound, or may contain two or more kinds.

[A1] polymer and [A2] crosslinkable compound may be used in combination in the resist underlayer film forming composition.

The content of the [A] compound in the composition for forming a resist lower layer film is preferably in a range of 0.1 to 10 parts by weight based on 100 parts by weight of the total solids in the resist underlayer film forming composition, The ratio of the content of the [A] compound to the total content is preferably 10 mass% or more, more preferably 30 mass% or more.

&Lt; Synthesis method of [A] compound >

The [A] compound having an organic sulfonyl group can be obtained, for example, by reacting a compound having a hydroxyl group and a compound for an organic sulfonylation in the presence of a base such as pyridine.

Among the above-mentioned reaction formulas (r-1) and (r-2), R is synonymous with the above formula (1). X is a halogen atom or a hydroxyl group.

In the above reaction formula (r-1), R ^x represents a structural unit of the polymer. n is an integer of 1 or more. na and nb are each independently an integer of 0 or more. na and nb satisfy na + nb = n.

In the above reaction formula (r-2), R ^y is a monovalent organic group.

The [A1] polymer can be obtained, for example, by reacting a polymer having a hydroxyl group with an organic sulfonylating reagent represented by R-SO ₂ -X as shown in the above reaction formula (r-1). Further, the [A2] crosslinkable compound can be prepared by reacting an organic sulfonylating reagent represented by R-SO ₂ -X with a compound R ^y -OH having a hydroxyl group, as shown by the above reaction formula (r-2) In an organic solvent.

The compound [A] wherein an organic sulfonyl group is bonded to a nitrogen atom can be obtained by using, for example, a compound having an amino group, an alkylamino group, a methylol group or an alkoxymethyl group-bonded amino group instead of the compound having a hydroxyl group .

The polymer [A1] is obtained by obtaining a monomer containing an organic sulfonyl group by using a hydroxyl compound having R ^y , which contains a polymerizable functional group such as an unsaturated bond, in the reaction formula (r-2) Can be synthesized by polymerization.

<[B] Solvent>

The resist underlayer film-forming composition usually contains a solvent. The solvent [B] is not particularly limited as long as it can dissolve the [A] compound.

As the [B] solvent, for example,

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether and ethylene glycol mono-n-butyl ether;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate and ethylene glycol mono-n-butyl ether acetate;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether and diethylene glycol di-n-butyl ether;

Triethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether and triethylene glycol diethyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether and propylene glycol di-n-butyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate;

Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, n-butyl lactate and i-butyl lactate;

Butyl formate, n-amyl formate, i-amyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-butyl acetate, isopropyl myristate, isopropyl myristate, Amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, n-butyl propionate, n-butyl propionate, propionic acid i Aliphatic carboxylic acid esters such as butyl, methyl butyrate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate and i-butyl butyrate;

Methyl propionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, 3- (2-hydroxyethyl) -2-methylpropionate, Methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methoxypropionyl acetate, Methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone;

Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;

and lactones such as? -butyrolactone.

Of these solvents, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, lactic acid esters, aliphatic carboxylic acid esters, other esters, ketones and lactones are preferable, and ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether, ethyl lactate, n-butyl acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Is more preferable. The solvent [B] may be used alone, or two or more solvents may be used in combination.

The content of the solvent [B] in the composition for forming a resist lower layer film is preferably 1 to 80 mass%, more preferably 3 to 40 mass%, still more preferably 5 By mass to 30% by mass.

<Other optional components>

The resin composition for forming a resist lower layer film may further contain [C] other crosslinking agent, [D] acid generator, [E] accelerator, [F] additive and the like, if necessary, as long as the effect of the present invention is not impaired . Among these, it is preferable that an [E] promoter is blended.

<[C] other crosslinking agent>

The resist underlayer film forming composition may contain other crosslinking agent in addition to the [A2] crosslinkable compound.

[C] Examples of other crosslinking agents include, for example, compounds having no organic sulfonyl group represented by the above formula (1) in the examples of the [A2] crosslinkable compound.

&Lt; [D] acid generator >

[D] The acid generator is a component which generates an acid by exposure or heating. The composition for forming a resist lower layer film contains the [D] acid generator, thereby enabling the cross-linking reaction to proceed more effectively between molecular chains of the [A] compound at a relatively low temperature including room temperature.

Examples of the acid generator (hereinafter also referred to as "photo acid generator") that generates an acid upon exposure include those described in paragraphs [0077] to [0081] in Japanese Patent Application Laid-Open No. 2004-168748 .

Of these photoacid generators, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium nonafluoro-n-butanesulfonate, diphenyl iodonium pyrenesulfonate, diphenyl iodonium n-dodecane Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalenesulfonate, bis (4- Butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4- Camphorsulfonate, and bis (4-t-butylphenyl) iodonium naphthalenesulfonate are preferable.

These photoacid generators may be used alone or in combination of two or more.

Examples of the acid generator (hereinafter referred to as &quot; thermal acid generator &quot;) that generates an acid upon heating include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2 - nitrobenzyl tosylate, alkyl sulfonates and the like.

These thermal acid generators may be used alone or in combination of two or more. As the acid generator [D], a photoacid generator and a thermal acid generator may be used in combination.

The content of the [D] acid generator in the composition for forming a resist lower layer film is generally 5,000 parts by mass or less, preferably 0.1 parts by mass to 1,000 parts by mass, more preferably 0.1 Parts by mass to 100 parts by mass.

<[E] Accelerator>

As the [E] promoter, there may be mentioned one electron oxidizer for sufficiently causing a dehydrogenation reaction required for oxidation crosslinking. 1 An electron oxidant means an oxidant that itself undergoes one electron transfer. For example, in the case of cerium (IV) nitrate ammonium, the cerium ion (IV) changes into cerium ion (III) by obtaining one electron. Further, a radical oxidizing agent such as a halogen produces one electron and is converted into an anion. As described above, the phenomenon of oxidizing the oxides by drawing one electron from the oxides (substrates, catalysts, etc.) is referred to as one electron oxidation, and the component that receives one electron at this time is referred to as one electron oxidizer.

Examples of the 1-electron oxidizing agent include (a) a metal compound, (b) a peroxide, (c) a diazo compound, and (d) a halogen or a halogen acid.

Examples of the metal compound (a) include metal compounds including cerium, lead, silver, manganese, osmium, ruthenium, vanadium, thallium, copper, iron, bismuth and nickel. Examples of such a metal compound include (a1) ammonium cerium (IV) nitrate (CAN), cerium (IV) acetate, cerium (IV) nitrate and cerium (IV) (For example, tetravalent lead compounds) such as cerium salts (for example, tetravalent cerium salts), (a2) lead tetraacetate and lead oxide (IV), (a3) silver oxide (I) (A4) manganese compounds such as permanganate, active manganese dioxide and manganese (III) salt, (a5) osmium compounds such as osmium tetraoxide, (a6) Ruthenium compounds such as ruthenium oxide, (a7) vanadium compounds such as VOCl ₃ , VOF ₃ , V ₂ O ₅ , NH ₄ VO ₃ and NaVO ₃ , (a8) thallium acetylacetonate, (II) trifluoromethanesulfonate, copper (II) trifluoroborate, copper (II) chloride, copper (II) acetate and copper ) Copper combination Water, iron compounds such as (a10) iron (III) chloride and potassium hexacyanoferrate (III), bismuth compounds such as (a11) sodium bismuthate, and (a12) nickel compounds such as nickel peroxide.

Examples of the peroxide (b) include peracids such as peracetic acid, m-chloroperbenzoic acid and the like; Hydroperoxides such as hydrogen peroxide and alkyl hydroperoxides such as t-butyl hydroperoxide; Diacyl peroxide, peracid ester, peracetic ketal, peroxyacetate, dialkyl peroxide, peracetic ketone and the like.

As the diazo compound (c), for example, 2,2'-azobisisobutyronitrile and the like can be given.

Examples of the halogen or the halogen acid (d) include halogens such as chlorine, bromine and iodine; And halogen acids, halogen acids, halogenated acids, halogenated acids and salts thereof. Examples of the halogen in the halogen acid include chlorine, bromine and iodine. Examples of the compound to be a halogen acid or a salt thereof include sodium perchlorate and sodium bromate.

Of these one electron oxidizing agent, (b) peroxide and (c) diazo compound are preferable, and m-chloro benzoic acid, t-butyl hydroperoxide and 2,2'-azobisisobutyronitrile are particularly preferable. When these are used, it is preferable because there is no possibility that metal residues adhere to the substrate. The [E] promoter may be used alone or in combination of two or more.

The content of the [E] promoter in the composition for forming a resist lower layer film is generally 1,000 parts by mass or less, preferably 0.01 parts by mass to 500 parts by mass, more preferably 0.1 parts by mass To 100 parts by mass.

<[F] Additive>

As the [F] additive, for example, those described in paragraphs [0088] to [0093] in Japanese Patent Application Laid-Open No. 2004-168748 can be used. As the [F] additive, for example, a binder resin, a radiation absorber, a surfactant, a storage stabilizer, a defoaming agent, and an adhesion aid may be mentioned.

As the binder resin, various thermoplastic resins and thermosetting resins (excluding the [A1] polymer) can be used. The thermoplastic resin is a component having an action to impart fluidity and mechanical properties of the added thermoplastic resin to the underlayer film. The thermosetting resin is a component which is cured by heating to be insoluble in a solvent and has a function of preventing intermixing between the resulting resist undercoat film and a resist film formed thereon, and can be preferably used as a binder resin. Of these, thermosetting resins such as urea resins, melamine resins, and aromatic hydrocarbon resins are preferred. These binder resins may be used alone or in combination of two or more.

The content of the binder resin is generally 20 parts by mass or less, preferably 10 parts by mass or less based on 100 parts by mass of the [A] compound in the composition for forming a resist lower layer film.

The content of the radiation absorbing agent is generally 100 parts by mass or less, preferably 50 parts by mass or less based on 100 parts by mass of the [A] compound of the composition for forming a resist lower layer film.

The surfactant is a component having an action to improve coating properties, stretching, wettability, developability and the like. These surfactants may be used alone or in combination of two or more.

The content of the surfactant is usually 15 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the polymer [A] in the resist underlayer film-forming resin composition.

&Lt; Process for producing a composition for forming a resist lower layer film &

The resist underlayer film forming composition can be produced, for example, by dissolving the [A] polymer and optional components as needed in the [B] solvent. After dissolution, the obtained solution is preferably filtered with a membrane filter having a pore size of about 0.1 占 퐉.

<Lower resist film>

The resist underlayer film of the present invention is formed from the resist underlayer film forming composition. The resist underlayer film is excellent in bending resistance and etching resistance, and as a result, has excellent pattern transfer performance to the substrate to be processed.

This resist undercoat film can be preferably used for a multilayer resist process. In the multilayer resist process, a resist undercoat film is formed on a substrate to be processed, a resist pattern is formed on the resist undercoat film, the resist pattern is once transferred to a resist undercoat film to form a resist undercoat film pattern, And transfers the pattern to the substrate to be processed using the pattern as an etching mask.

The hydrogen atom content of the resist underlayer film is preferably 0 to 50 atomic%, more preferably 0 to 35 atomic%. The hydrogen atom content in the resist underlayer film can be obtained by measuring the element composition of the resist underlayer film with respect to carbon, hydrogen and nitrogen.

&Lt; Method of forming lower resist film &

The method for forming a resist underlayer film of the present invention comprises the steps of (1) applying a composition for forming a resist lower layer film on a substrate to form a coating film, and (2) heating the coating film to form a resist underlayer film .

As the substrate to be processed, for example, a silicon wafer, a wafer coated with aluminum, or the like can be used. The method of applying the composition for forming a resist lower layer film on the substrate to be processed is not particularly limited and may be carried out by any appropriate method such as spin coating, soft coating or roll coating.

The heating of the coating film is usually carried out in the atmosphere. The heating temperature is usually 300 ° C to 500 ° C, preferably 350 ° C to 450 ° C or so. If the heating temperature is lower than 300 占 폚, the oxidation crosslinking does not proceed sufficiently and the properties required for the resist underlayer film may not be exhibited. The heating time is usually 30 seconds to 1200 seconds, preferably 60 seconds to 600 seconds.

The oxygen concentration at the time of coating film curing is preferably 5 vol% or more. When the oxygen concentration at the time of coating film formation is low, oxidation crosslinking of the resist lower layer film does not progress sufficiently, and there is a fear that required properties as a resist lower layer film may not be developed.

The coating film may be preliminarily heated at a temperature of 60 ° C to 250 ° C before being heated at a temperature of 300 ° C to 500 ° C. The heating time in the preliminary heating is not particularly limited, but is preferably 10 seconds to 300 seconds, and more preferably 30 seconds to 180 seconds. By carrying out the preliminary heating, the solvent is vaporized in advance and the film is made dense, so that the dehydrogenation reaction can proceed efficiently.

In the method of forming the resist underlayer film, the coating film is usually cured by heating the coating film to form a resist underlayer film. However, by containing a predetermined photo-curing agent (crosslinking agent) in the resist underlayer film forming composition, A resist undercoat film may be formed by photocuring the resist film. The radiation exposed at this time is appropriately selected from visible light, ultraviolet light, far ultraviolet ray, X-ray, electron beam, γ-ray, molecular beam, ion beam, etc. depending on the kind of the acid generator [D] do.

&Lt; Pattern formation method >

(1) a resist lower layer film forming step (hereinafter referred to as &quot; step (1) &quot;) for forming a resist lower layer film on the upper side of the substrate to be processed by using the composition for lower layer film formation; ) (2) a resist film forming step (hereinafter, also referred to as "step (2)") in which a resist composition is applied on the resist lower layer film to form a resist film; (3) (Hereinafter, also referred to as &quot; process (3) &quot;) for exposing a resist film by irradiating the resist film with radiation, (4) a step of forming a resist pattern by developing the exposed resist film (4) "), and (5) the resist pattern is used as a mask, and the resist lower layer film and the substrate to be processed are sequentially dry- It has the pattern forming process (hereinafter also referred to as "step (5)") for forming a predetermined pattern on a substrate to be processed.

In step (1), a resist underlayer film is formed on the upper side of the substrate to be processed by using a composition for forming a resist lower layer film. The method for forming the resist lower layer film can be applied to the above description as it is. The film thickness of the resist lower layer film formed in this step (1) is usually 0.05 탆 to 5 탆.

Further, in this pattern forming method, after the step (1), it may further have a step (1 ') of forming an intermediate layer (intermediate coating film) on the resist lower layer film if necessary. This intermediate layer is a layer imparted with such a function to further supplement the functions of the resist underlayer film and / or the resist coat in forming a resist pattern, or to provide them with a function not possessed by them. For example, when the antireflection film is formed as an intermediate layer, the antireflection function of the resist underlayer film can be further supplemented.

The intermediate layer may be formed of an organic compound or an inorganic oxide. DUV-42, DUV-44, ARC-28, and ARC-29 (manufactured by Brewer Science, Inc.); AR-3 &quot;, &quot; AR-19 &quot; (manufactured by Rohm and Haas), and the like. Examples of the inorganic oxide include commercially available products such as "NFC SOG01", "NFC SOG04", and "NFC SOG080" (manufactured by JSR Corporation). In addition, polysiloxane, titanium oxide, alumina oxide, tungsten oxide, or the like formed by the CVD method can be used.

The method for forming the intermediate layer is not particularly limited, and for example, a coating method, a CVD method, or the like can be used. Of these, a coating method is preferable. When the coating method is used, the intermediate layer can be formed continuously after the resist lower layer film is formed.

The thickness of the intermediate layer is not particularly limited and is appropriately selected according to the function required for the intermediate layer, but is preferably from 10 nm to 3,000 nm, more preferably from 20 nm to 300 nm.

In the step (2), a resist composition is applied on the resist underlayer film to form a resist film. Specifically, a resist composition is applied so that the obtained resist coating film has a predetermined film thickness, and then the resist film is baked by volatilizing the solvent in the coating film by prebaking.

Examples of the resist composition include a positive-type or negative-type chemically amplified resist composition containing a photoacid generator, a positive resist composition containing an alkali-soluble resin and a quinonediazide-based photosensitizer, an alkali-soluble resin and a crosslinking agent , And the like.

The total solid concentration of the resist composition is usually about 1 to 50% by mass. Further, the resist composition is generally provided for forming a resist coating film by, for example, filtration through a filter having a pore size of about 0.2 mu m. In this step, commercially available resist compositions may be used as they are.

The method of applying the resist composition is not particularly limited, and for example, a spin coating method and the like can be given. The temperature for prebaking is appropriately adjusted according to the type of the resist composition to be used, and is usually about 30 to 200 캜, preferably 50 to 150 캜.

In the step (3), the resist film is selectively irradiated with radiation to expose the resist film. The radiation used for the exposure is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam,? -Ray, molecular beam, ion beam and the like depending on the kind of the photoacid generator used in the resist composition. Of these, far ultraviolet light is preferable and KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ excimer laser light (157 nm wavelength), Kr ₂ excimer laser light Excimer laser light (wavelength: 134 nm), and ultraviolet light (wavelength: 13 nm). In addition, the resist pattern forming method may not be a developing step such as a nanoimprint method.

Post-baking can be performed after the exposure in order to improve resolution, pattern profile, developability and the like. The post baking temperature is appropriately adjusted according to the type of the resist composition to be used, and is usually about 50 캜 to 200 캜, preferably 70 캜 to 150 캜.

In step (4), the exposed resist film is developed to form a resist pattern. The developer used in this step is appropriately selected depending on the kind of the resist composition to be used. Examples of the developer include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, Diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7- undecene, And alkaline aqueous solutions such as 5-diazabicyclo [4.3.0] -5-nonene and the like. To these alkaline aqueous solutions, water-soluble organic solvents such as alcohols such as methanol and ethanol, surfactants and the like may be added in an appropriate amount.

After development in the developer, the resist is washed and dried to form a predetermined resist pattern.

In step (5), the resist underlayer film and the substrate to be processed are sequentially dry-etched using the resist pattern as a mask to form a predetermined pattern on the substrate to be processed. For this dry etching, for example, gas plasma such as oxygen plasma is used. After dry etching of the resist lower layer film, the substrate to be processed is dry-etched to obtain a processed substrate having a predetermined pattern.

As a pattern forming method using the composition for forming a resist lower layer film, a pattern forming method using, for example, a nanoimprint method or the like can be mentioned in addition to the pattern forming method described above.

[Example]

Hereinafter, the present invention will be described concretely based on examples, but the present invention is not limited to these examples. The measurement of the physical properties in this example was carried out according to the following method.

[Weight average molecular weight (Mw)]

The Mw of the polymer was measured using a GPC column (G2000HXL: 2, G3000HXL: 1 (manufactured by Tosoh Corporation)) at a flow rate of 1.0 mL / min, an eluting solvent of tetrahydrofuran, a column temperature of 40 DEG C, , And a gel permeation chromatograph using monodispersed polystyrene as a standard.

&Lt; Synthesis of [A] compound >

[Synthesis Example 1]

100 parts by mass of 2,7-dihydroxynaphthalene, 200 parts by mass of propylene glycol monomethyl ether acetate and 50 parts by mass of paraformaldehyde were fed into a reaction apparatus equipped with a condenser, a thermometer and a stirrer, 2 parts by mass of oxalic acid was added, After raising the temperature to 120 캜 while dehydrating, the reaction was carried out for 5 hours to obtain a polymer (a1-1). Thereafter, 300 parts by mass of paratoluene sulfonyl chloride and 50 parts by mass of pyridine were added to obtain a polymer (A1-1) having a structure represented by the following formula (A1-1) as a condensation reaction product. The Mw of this polymer (A1-1) was 3,000.

[Synthesis Example 2]

100 parts by mass of 2-hydroxynaphthalene, 200 parts by mass of propylene glycol monomethyl ether acetate and 50 parts by mass of paraformaldehyde were charged into a reaction apparatus equipped with a condenser, a thermometer and a stirrer, 2 parts by mass of oxalic acid was added, Lt; 0 &gt; C, and reacted for 5 hours. Thereafter, 300 parts by mass of para-toluene sulfonyl chloride and 50 parts by mass of pyridine were added to obtain a polymer (A1-2) having a structure represented by the following formula (A1-2) as a condensation reaction product. The Mw of this polymer (A1-2) was 3,000.

[Synthesis Example 3]

100 parts by mass of phenol, 200 parts by mass of propylene glycol monomethyl ether acetate and 50 parts by mass of paraformaldehyde were fed into a reactor equipped with a condenser, a thermometer and a stirring device, 2 parts by mass of oxalic acid was added, Thereafter, reaction was carried out for 5 hours to obtain a polymer (a1-2). Thereafter, 300 parts by mass of paratoluene sulfonyl chloride and 50 parts by mass of pyridine were added to obtain a polymer (A1-3) having a structure represented by the following formula (A1-3) which is a condensation reaction product. The Mw of this polymer (A1-3) was 5,000.

[Synthesis Example 4]

100 parts by mass of phenol, 200 parts by mass of propylene glycol monomethyl ether acetate and 50 parts by mass of paraformaldehyde were fed into a reactor equipped with a condenser, a thermometer and a stirring device, 2 parts by mass of oxalic acid was added, Then, the reaction was carried out for 5 hours. Thereafter, 300 parts by mass of 2-thiophenesulfonyl chloride and 50 parts by mass of pyridine were added to obtain a polymer (A1-4) having a structure represented by the following formula (A1-4) as a condensation reaction product. The Mw of this polymer (A1-4) was 5,000.

[Synthesis Example 5]

100 parts by mass of p-hydroxystyrene, 200 parts by mass of propylene glycol monomethyl ether and 50 parts by mass of paraformaldehyde were fed into a reaction apparatus equipped with a condenser, a thermometer and a stirrer, 2 parts by mass of oxalic acid was added, And allowed to react for 5 hours. Thereafter, 300 parts by mass of 2-thiophenesulfonyl chloride and 50 parts by mass of pyridine were added to obtain a polymer (A1-5) having a structure represented by the following formula (A1-5) which is a condensation reaction product. The Mw of this polymer (A1-5) was 5,000.

[Synthesis Example 6]

A reactor equipped with a condenser, a thermometer and a stirrer was charged with 100 parts by mass of 4,4 '- [1- [4- [2- (4-hydroxyphenyl) propan-2- yl] phenyl] ethylidene] , 200 parts by mass of propylene glycol monomethyl ether acetate and 50 parts by mass of paraformaldehyde were charged, and 2 parts by mass of oxalic acid was added. The mixture was heated to 120 DEG C while dehydrating, and reacted for 5 hours. Thereafter, 300 parts by mass of 2-thiophenesulfonyl chloride and 50 parts by mass of pyridine were added to obtain a compound (A2-1) having a structure represented by the following formula (A2-1).

[Synthesis Example 7]

125 parts by mass of the polymer (a1-1) obtained as an intermediate in Synthesis Example 1, 25 parts by mass of thiophene methanol, 20 parts by mass of p-toluenesulfonic acid and 150 parts by mass of methyl isobutyl ketone 150 And the mixture was heated to 100 캜 and reacted for 4 hours to obtain a polymer (a1-3) having a structure represented by the following formula (a1-3). The Mw of this polymer (a1-3) was 3,000.

&Lt; Preparation of a composition for forming a resist lower layer film &

[Example 1]

100 parts by mass of the polymer (A1-1) as the [A] compound and 0.005 parts by mass of the surfactant were dissolved in 450 parts by mass of cyclohexanone as the [B] solvent. Thereafter, this solution was filtered with a membrane filter having a pore size of 0.1 탆 to prepare a composition for forming a resist lower layer film of Example 1.

[Examples 2 to 7 and Comparative Examples 1 to 3]

A composition for forming a resist lower layer film in each of Examples and Comparative Examples was prepared in the same manner as in Example 1 except that the kind and the amount of the compound [A] in Example 1 were changed as shown in Table 1 below. The polymer (a1-1) used in Example 6 and Comparative Example 1 was shown as an intermediate in Synthesis Example 1, and the polymer (a1-2) used in Example 7 and Comparative Example 2 was the same as that shown in Synthesis Example 3 will be.

<Evaluation>

Using the compositions for forming the resist lower layer films obtained in the above Examples and Comparative Examples, a resist lower layer film was formed by the following method, and element composition, pattern transfer performance, etching resistance and sulfur-containing outgassing resistance were measured by the following methods Respectively. The evaluation results are shown in Table 1.

[Formation of resist lower layer film]

On the silicon wafer having a diameter of 8 inches, the obtained composition for forming a resist lower layer film was applied by spin coating. Then, it was heated at 180 캜 for 60 seconds in a hot plate with an oxygen concentration of 20% by volume. Subsequently, the resist underlayer was heated at 350 DEG C for 120 seconds to form a resist undercoat film having a thickness of 0.3 mu m.

[Bending resistance]

A silicon-containing intermediate layer-forming composition (NFC SOG080, manufactured by JSR Corporation) for three-layer resist processing was spin-coated on the formed resist underlayer film and heated on a hot plate at 300 캜 for 60 seconds to form an intermediate layer coating film having a thickness of 0.05 탆 . Subsequently, a resist composition for ArF (ARF AR2772JN, manufactured by JSR) was spin coated on the intermediate layer coating and prebaked on a hot plate at 130 캜 for 90 seconds to form a resist coating film having a thickness of 0.2 탆.

Thereafter, the resist film was exposed through a photomask having a predetermined mask pattern formed thereon using an ArF excimer laser exposure apparatus (NSR-S610C, manufactured by NIKON, lens numerical aperture: 1.30, exposure wavelength: 193 nm). Thereafter, post baking was performed for 90 seconds on a hot plate at 130 캜. Next, using a tetramethylammonium hydroxide aqueous solution having a concentration of 2.38%, it was developed at 25 占 폚 for 1 minute. Thereafter, the resist pattern was washed with water and dried to obtain a positive resist pattern (line and space pattern (1L / 1S) having a line width of 40 nm). Using this resist pattern as a mask, dry etching was performed using an etching apparatus (Telius SCCM, Tokyo Electron, conditions: etching gas CF ₄ / Ar (CF ₄ : 200 mL / min, RF power: 300 W) , And the resist pattern was transferred to the intermediate layer coating.

Next, an etching gas O ₂ / N ₂ (O ₂ : 50 mL / min, N ₂ : 50 mL / min, RF power: 700 W), and the pattern was transferred to the resist lower layer film. Subsequently, an etching gas CF ₄ / Ar (CF ₄ : 200 mL / min, Ar: 400 mL / min, RF power: 1000 W) was etched using the above etching apparatus, , And the pattern was transferred to a SiO ₂ substrate (silicon wafer having a diameter of 8 inches).

The pattern shape of the resist underlayer film was observed with a scanning electron microscope (SEM) (CG-4000, manufactured by Hitachi High-Technologies Corporation) from the upper side before and after the etching operation on the SiO ₂ substrate. The line width in each pattern was measured at 10 points at arbitrary points, and the value obtained by expressing the variation of the line width with 3 sigma was defined as LWR (Line Width Roughness). The bending resistance of the resist underlayer film was evaluated by the following criteria.

A: The LWR of the resist underlayer film pattern after etching is equal to or better than that before etching for the SiO ₂ substrate

B: LWR of the resist underlayer film pattern deteriorated after etching, as compared with before etching for SiO ₂ substrate

[Etching Resistance]

The formed resist lower layer film was etched under the conditions of CF ₄ / Ar (CF ₄ : 40 mL / min, Ar: 20 mL / min; RF power: 200 W) using an etching apparatus (EXAM, Treatment. At this time, the etching rate (unit: nm / minute) was calculated from the film thickness measurement values before and after the etching treatment, and the etching resistance was evaluated.

[Sulfur Containing Outgass Repellency]

On the silicon wafer having a diameter of 8 inches, a composition for forming a resist lower layer film was applied by spin coating. The wafer coated with the composition for forming a resist lower layer film was heated to 250 DEG C by using headspace gas chromatography (HS-GC), and the sulfide Or the sulfur content (% by mass) contained as thiols was measured.

Based on the sulfur content in the obtained outgas, the sulfur-containing outgas suppressibility was evaluated according to the following criteria.

A: The sulfur content in the outgass was lower than that in Comparative Example 3

B: The sulfur content in the outgas was equal to or higher than that in Comparative Example 3

The results obtained in the above evaluation are shown in Table 1 below.

From the results of the above Examples and Comparative Examples, it was found that the lower layer film forming composition of the present invention can form a resist lower layer film having excellent bend tolerance and pattern transfer performance in RIE and excellent etching resistance. In addition, as compared with the thiophene lower layer film material of Comparative Example 3, outgas at the time of forming the lower layer film could be stinked.

The composition for forming a resist lower layer film of the present invention is preferably used as a material for forming a resist lower layer film used in a multilayer resist process preferable for microfabrication in the lithography process, particularly in the manufacture of highly integrated circuit devices.

Claims (14)

(A) a compound represented by the following general formula (1), at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings, A resist underlayer film forming step of forming a resist underlayer film on the upper side of the substrate to be processed by using a composition for forming a resist lower layer film containing a compound bonded to the ring via an oxygen atom,
(2) Applying a resist composition onto the resist lower layer film to form a resist film
A resist film forming step of forming a resist film,
(3) an exposure step for selectively exposing the resist film to radiation to expose the resist film,
(4) a resist pattern forming step of developing the exposed resist film to form a resist pattern, and
(5) a pattern forming step of using the resist pattern as a mask, successively dry-etching the resist underlayer film and the substrate to form a predetermined pattern on the substrate to be processed
&Lt; / RTI >
&Lt; Formula 1 &gt;

(Wherein R represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a heterocyclic group having 3 to 15 carbon atoms, An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an aryloxy group, an aryloxy carbonyl group, an amide group, an alkyl amide group or an aryl amide group of 6 to 30 A cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a heterocyclic group having 3 to 15 carbon atoms, a fluorine atom, a chlorine atom , Bromine atom, iodine atom, hydroxyl group, amino group, carboxyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, arylcarboxy group, aryloxycarbonyl , An amide group, and at least one kind of group that is an alkyl amide group or aryl amide group selected from the group consisting of groups 3 to 30 in carbon number can also have a heteroaryl as a substituent, and * represents a bonding hand) The method according to claim 1, further comprising: (1) between the resist lower layer film forming step and (2)
(1 ') an intermediate layer forming step of forming an intermediate layer on the upper surface side of the resist lower layer film
Lt; / RTI &gt;
(5) In the pattern forming step, the intermediate layer is further subjected to dry etching. delete delete The pattern forming method according to claim 1 or 2, wherein the compound [A] has a partial structure represented by the following formula (2).
(2)

(Wherein, Q is an aromatic ring or heteroaromatic ring, R is the same as in the above formula (1), Y is an oxygen atom, n0 is an integer of 1 or more, R ¹ is a monovalent organic group, Provided that when R, Y and R ¹ are each plural, plural R, Y and R ¹ may be the same or different, 6. The method according to claim 5, wherein the [A] compound is a polymer. The pattern forming method according to claim 6, wherein the polymer is at least one resin selected from the group consisting of a novolac resin, a resol resin, a styrene resin, an acenaphthylene resin and a polyarylene resin. The pattern forming method according to claim 5, wherein the [A] compound is a crosslinkable compound. The pattern forming method according to claim 1 or 2, further comprising a [B] solvent. (A) a compound represented by the following general formula (1), at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings, A step of applying a composition for forming a resist lower layer film containing a compound bonded to a ring through an oxygen atom to form a coating film on the substrate;
(2) a step of forming the resist underlayer film by heating the above-mentioned coating film
Of the resist underlayer film.
&Lt; Formula 1 >

(Wherein R represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a heterocyclic group having 3 to 15 carbon atoms, An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an aryloxy group, an aryloxy carbonyl group, an amide group, an alkyl amide group or an aryl amide group of 6 to 30 A cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a heterocyclic group having 3 to 15 carbon atoms, a fluorine atom, a chlorine atom , Bromine atom, iodine atom, hydroxyl group, amino group, carboxyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, arylcarboxy group, aryloxycarbonyl , An amide group, and at least one kind of group that is an alkyl amide group or aryl amide group selected from the group consisting of groups 3 to 30 in carbon number can also have a heteroaryl as a substituent, and * represents a bonding hand) [A] a compound represented by the following formula (1), at least one ring selected from the group consisting of an aromatic ring and a heteroaromatic ring and having a bond represented by * in the group represented by the following formula (1) A composition for forming a resist lower layer film containing a compound bonded via an atom.
&Lt; Formula 1 >

(Wherein R represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a heterocyclic group having 3 to 15 carbon atoms, An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an aryloxy group, an aryloxy carbonyl group, an amide group, an alkyl amide group or an aryl amide group of 6 to 30 A cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a heterocyclic group having 3 to 15 carbon atoms, a fluorine atom, a chlorine atom , Bromine atom, iodine atom, hydroxyl group, amino group, carboxyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, arylcarboxy group, aryloxycarbonyl , An amide group, and at least one kind of group that is an alkyl amide group or aryl amide group selected from the group consisting of groups 3 to 30 in carbon number can also have a heteroaryl as a substituent, and * represents a bonding hand) delete delete A resist underlayer film formed from the composition for forming a resist lower layer film according to claim 11.