JP6885281B2 - A composition for forming a resist underlayer film, a method for forming a resist underlayer film, a method for forming a resist underlayer film, and a method for producing a patterned substrate. - Google Patents

Description

The present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a method for forming a resist underlayer film, a method for producing a patterned substrate, and a compound.

In the manufacture of semiconductor devices, a multilayer resist process is used to obtain a high degree of integration. In this process, a resist underlayer film forming composition is first applied to one surface side of the substrate, and then the resist underlayer film to be formed is heated to form a resist underlayer film, and the upper surface of the resist underlayer film is formed. A resist pattern is formed on the side using a resist composition or the like. Next, the resist underlayer film is etched using this resist pattern as a mask, and the substrate is further etched using the obtained resist underlayer film pattern as a mask to form a desired pattern on the substrate to obtain a patterned substrate. it can. The resist underlayer film used in such a multilayer resist process is required to have general properties such as solvent resistance and etching resistance.

Recently, there has been an increasing number of cases where a pattern is formed on a substrate having a plurality of types of trenches, particularly trenches having different aspect ratios from each other. In this case, the resist underlayer film forming composition used for forming the resist underlayer film is required to be able to sufficiently embed these trenches and to have high flatness.

Further, in a multilayer resist process, a method of forming a hard mask as an intermediate layer on a resist underlayer film has recently been studied. In this method, specifically, since the inorganic hard mask is formed on the resist underlayer film by the CVD method, the temperature is at least 300 ° C., usually 400 ° C. or higher, particularly in the case of a nitride-based inorganic hard mask. Therefore, the resist underlayer film needs to have high heat resistance. If the heat resistance is insufficient, the components of the resist underlayer film sublimate, and the sublimated components reattach to the substrate, which has the disadvantage of lowering the manufacturing yield of the semiconductor device. Further, in the multilayer resist process, improvement of solvent resistance and etching resistance is also desired.

In response to these demands, various studies have been conducted on the structure of polymers and the like contained in the composition for forming a resist underlayer film and the functional groups contained therein (see JP-A-2004-177668). However, the above-mentioned conventional resist underlayer film forming composition cannot sufficiently satisfy these requirements.

Japanese Unexamined Patent Publication No. 2004-177668

The present invention has been made based on the above circumstances, and an object thereof is for forming a resist underlayer film capable of forming a resist underlayer film having excellent heat resistance and flatness, as well as excellent solvent resistance and etching resistance. It is an object of the present invention to provide a composition, a resist underlayer film, a method for forming a resist underlayer film, a method for producing a patterned substrate, and a compound.

The invention made to solve the above-mentioned problems contains a compound represented by the following formula (1) and a solvent, and the above-mentioned compound with respect to the total peak area (Aa) measured by gel permeation chromatography. This is a composition for forming a resist underlayer film in which the ratio of the peak area (A1) of the peaks contained is 0.25 or more.

（式（１）中、Ｒ^１及びＲ^１０は、それぞれ独立して、水素原子又は炭素数１〜３０の１価の有機基である。Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立して、ヒドロキシ基、ハロゲン原子又は炭素数１〜２０の１価の有機基である。ｎ１及びｎ４は、０〜５の整数である。ｎ２及びｎ３は、０〜４の整数である。但し、ｎ１＋ｎ２＋ｎ３＋ｎ４≧１である。ｎ１が２以上の場合、複数のＲ^２は、同一でも異なっていてもよい。ｎ２が２以上の場合、複数のＲ^３は、同一でも異なっていてもよい。ｎ３が２以上の場合、複数のＲ^４は、同一でも異なっていてもよい。ｎ４が２以上の場合、複数のＲ^５は、同一でも異なっていてもよい。）

(In the formula (1), R ¹ and R ¹⁰ are independently hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ are respectively. Independently, it is a hydroxy group, a halogen atom or a monovalent organic group having 1 to 20 carbon atoms. N1 and n4 are integers of 0 to 5. n2 and n3 are integers of 0 to 4. However, in the case of n1 + n2 + n3 + n4 ≧ 1 and is .n1 is 2 or more, plural ^{R 2} may, if may be the same or different .n2 is 2 or more, plural ^{R 3} may be the same or different. If n3 is 2 or more, plural R ^4, if may be the same or different .n4 is 2 or more, plural R ⁵ may be the same or different.)

Yet another invention made to solve the above problems is a resist underlayer film formed from the resist underlayer film forming composition.

Yet another invention made to solve the above problems is a step of applying the resist underlayer film forming composition on at least one surface side of the substrate, and a coating film formed by the coating step. It is a method of forming a resist underlayer film including a step of heating.

Yet another invention made to solve the above problems is a step of forming a resist pattern on the surface side of the resist underlayer film formed by the method for forming the resist underlayer film opposite to the substrate, and the resist pattern. This is a method for manufacturing a patterned substrate, which comprises a step of performing etching using the above as a mask.

Yet another invention made to solve the above problems is a compound represented by the following formula (1).

（式（１）中、Ｒ^１及びＲ^１０は、それぞれ独立して、水素原子又は炭素数１〜３０の１価の有機基である。Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立して、ヒドロキシ基、ハロゲン原子又は炭素数１〜２０の１価の有機基である。ｎ１及びｎ４は、０〜５の整数である。ｎ２及びｎ３は、０〜４の整数である。但し、ｎ１＋ｎ２＋ｎ３＋ｎ４≧１である。ｎ１が２以上の場合、複数のＲ^２は、同一でも異なっていてもよい。ｎ２が２以上の場合、複数のＲ^３は、同一でも異なっていてもよい。ｎ３が２以上の場合、複数のＲ^４は、同一でも異なっていてもよい。ｎ４が２以上の場合、複数のＲ^５は、同一でも異なっていてもよい。）

(In the formula (1), R ¹ and R ¹⁰ are independently hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ are respectively. Independently, it is a hydroxy group, a halogen atom or a monovalent organic group having 1 to 20 carbon atoms. N1 and n4 are integers of 0 to 5. n2 and n3 are integers of 0 to 4. However, in the case of n1 + n2 + n3 + n4 ≧ 1 and is .n1 is 2 or more, plural ^{R 2} may, if may be the same or different .n2 is 2 or more, plural ^{R 3} may be the same or different. If n3 is 2 or more, plural R ^4, if may be the same or different .n4 is 2 or more, plural R ⁵ may be the same or different.)

The resist underlayer film forming composition of the present invention can form a resist underlayer film having excellent heat resistance and flatness, as well as excellent solvent resistance and etching resistance. The resist underlayer film of the present invention is excellent in heat resistance and flatness, as well as solvent resistance and etching resistance. According to the method for forming a resist underlayer film of the present invention, it is possible to form a resist underlayer film having excellent heat resistance and flatness, as well as excellent solvent resistance and etching resistance. According to the method for producing a patterned substrate of the present invention, the resist underlayer film is formed by using the method for forming the resist underlayer film, so that a substrate having an excellent pattern shape can be obtained. The compound of the present invention can be suitably used as a component of the composition for forming a resist underlayer film. Therefore, these can be suitably used for manufacturing semiconductor devices and the like, which are expected to be further miniaturized in the future.

It is a schematic cross-sectional view for demonstrating the evaluation method of flatness. It is a figure explaining the evaluation method of the ratio of the peak area (A1) of the peak containing the said compound with respect to the total peak area (Aa) measured by gel permeation chromatography (GPC). It is a figure which shows the chart by GPC analysis of the composition for forming a resist underlayer film J-1. It is a figure which shows the chart by GPC analysis of the composition for forming a resist underlayer film J-2. It is a figure which shows the chart by GPC analysis of the composition for forming a resist underlayer film J-5. It is a figure which shows the chart by GPC analysis of the composition for forming a resist underlayer film CJ-2.

<Composition for forming a resist underlayer film>
The resist underlayer film forming composition contains a compound represented by the following formula (1) (hereinafter, also referred to as “[A] compound”) and a solvent (hereinafter, also referred to as “[B] solvent”). .. The resist underlayer film forming composition contains an acid generator (hereinafter, also referred to as “[C] acid generator”) and / or a cross-linking agent (hereinafter, also referred to as “[D] cross-linking agent”). It may contain other optional components as long as the effect of the present invention is not impaired. Each component will be described below.

<[A] Compound>
The compound [A] is a compound (A) represented by the following formula (1). As the compound (A), one kind or two or more kinds can be used.

By containing the compound [A], the resist underlayer film forming composition can form a resist underlayer film having excellent heat resistance and flatness, as well as solvent resistance and etching resistance. The reason why the resist underlayer film forming composition has the above-mentioned effect is not always clear, but it can be inferred as follows, for example. That is, since the compound (A) is a relatively low-molecular-weight compound having a pyrene skeleton, the embedding property is good. As a result, it is considered that the flatness of the resist underlayer film forming composition is improved. Further, since the compound (A) contains the compound (A) represented by the following formula (1), the resist underlayer film is excellent in sublimation inhibitory property at high temperature when heated, and the solvent resistance of the formed film is excellent. It is considered that the etching resistance and heat resistance are improved.

[Compound (A)]
Compound (A) is a compound represented by the following formula (1).

In the above formula (1) and in the formula (1), R ¹ and R ¹⁰ are independently hydrogen atoms or monovalent organic groups having 1 to 30 carbon atoms. R ^{2, R} 3, ^{R 4} and ^{R 5} are hydroxy group, a monovalent organic group having a halogen atom or having 1 to 20 carbon atoms.

n1 and n4 are integers from 0 to 5. n2 and n3 are integers from 0 to 4. However, n1, n2, n3 and n4 are n1 + n2 + n3 + n4 ≧ 1, preferably n1 + n2 ≧ 1 or n3 + n4 ≧ 1, preferably n1 + n2 + n3 + n4 ≧ 2, and more preferably n1 + n2 ≧ 1 and n3 + n4 ≧ 1. If n1 is 2 or more, plural R ² may be the same or different. If n2 is 2 or more, plural R ³ may be the same or different. If n3 is 2 or more, plural R ⁴ may be the same or different. If n4 is 2 or more, plural R ^5, may be the same or different.

Examples of the monovalent organic group having 1 to 30 carbon atoms represented by R ¹ and R ¹⁰ include a monovalent hydrocarbon group having 1 to 30 carbon atoms, a carbon-carbon group of this hydrocarbon group, or this hydrocarbon. A group ^{(α) containing a divalent heteroatom-containing group between the group and the carbon atom to which R 1} and R ¹⁰ are bonded, and a part or all of the hydrogen atoms of the above hydrocarbon group and group (α) are 1 Examples thereof include a group substituted with a valent heteroatom-containing group.

Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a tert-amyl group and an n-hexyl group. ,
An alkenyl group having 1 to 30 carbon atoms, such as an ethenyl group, a propenyl group, and a butenyl group,
A chain hydrocarbon group having 1 to 30 carbon atoms, such as an alkynyl group such as an ethynyl group, a propynyl group, or a butynyl group,
Cycloalkyl groups such as cyclopentyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, etc.
Cycloalkenyl groups having 1 to 30 carbon atoms, such as cyclopropenyl group, cyclopentenyl group, cyclohexenyl group, etc.
Alicyclic hydrocarbon groups having 1 to 30 carbon atoms, such as bridging ring hydrocarbon groups such as norbornyl group and adamantyl group.
A monovalent aryl group having 1 to 30 carbon atoms such as a phenyl group, a methylphenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthryl group, a phenanthryl group and a pyrenyl group.
Aralkyl groups having 1 to 30 carbon atoms such as benzyl group, phenethyl group and naphthylmethyl group,
Styryl group, styrylmethyl group, vinylbenzyl group, acenaphthyl group, acenaphthylmethyl group,
Examples thereof include groups having an aromatic hydrocarbon group having 1 to 30 carbon atoms such as a ring-assembled aromatic hydrocarbon group such as a biphenyl group, a terphenyl group and a binaphthyl group.

Examples of the divalent heteroatom-containing group include -CO-, -CS-, -NH-, -O-, -S-, and a group combining these. Of these, -O- and -CO- are preferable.

Examples of the group (α) containing a divalent heteroatom-containing group between carbon-carbon of the hydrocarbon group or between the hydrocarbon group and ^{the carbon atom to which R 1} and R ^{10 are bonded include an oxoalkyl group and a thioalkyl group.} , Alkylaminoalkyl groups, alkoxyalkyl groups, alkylthioalkyl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups and other heteroatomic chain groups,
Heteroatom-containing cyclic groups such as oxocycloalkyl groups, thiocycloalkyl groups, azacycloalkyl groups, oxacycloalkyl groups, thiacycloalkyl groups, oxocycloalkenyl groups, and oxathiacycloalkyl groups,
Hydrocarbyloxy group containing aromatic hydrocarbon groups such as styryloxy group, styrylmethyloxy group, vinylbenzyloxy group, acenaphthyloxy group, acenaphthylmethyloxy group, etc.
Examples thereof include aromatic heterocyclic groups such as heteroaryl groups such as pyrrolyl group, pyridyl group, quinolyl group, isoquinolyl group, furyl group, pyranyl group, thienyl group and benzothiophenyl group.
Among these, a group containing —O— or −CO— between carbon-carbon of the hydrocarbon group or between the hydrocarbon group and ^{the carbon atom to which R 1} and R ¹⁰ are bonded is preferable, and for example, an alkoxyalkyl group, Examples thereof include a polyalkoxyalkyl group and an alkoxy (polyoxyalkylene) alkyl group.

Examples of the monovalent heteroatom-containing group include a hydroxy group, a sulfanyl group, a cyano group, a nitro group, a halogen atom and the like.

Examples of the group in which a part or all of the hydrogen atoms of the hydrocarbon group and the group (α) are substituted with a monovalent heteroatom-containing group include a hydroxyaryl group, an alkoxyaryl group, an allyloxyaryl group, and a propargyloxyaryl group. , Phenoxyaryl group, aryl halide group, alkylaryl halide group, aralkyl halide group, alkyl aralkyl halide group and the like.

The monovalent organic group having 1 to 30 carbon atoms represented by R ¹ and R ^10, a group of at least one has an aromatic ring of the above organic group of R ¹ and R ^10, chain hydrocarbon group And a group containing -O- or -CO- between carbon-carbon of the hydrocarbon group or between the hydrocarbon group and ^{the carbon atom to which R 1} and R ¹⁰ are bonded is preferable, and an aryl group and a ring-assembled aromatic carbide are preferable. Hydrogen groups, alkyl groups and alkoxy (polyoxyalkylene) alkyl groups are more preferred.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ² , R ³ , R ⁴ and R ⁵ include a monovalent hydrocarbon group having 1 to 20 carbon atoms and the carbon of this hydrocarbon group. A group (α) containing a divalent heteroatom-containing group between carbons or between the hydrocarbon group and ^{the carbon atom to which R 2 to} R ⁵ are bonded, and a hydrogen atom contained in the above-mentioned hydrocarbon group and group (α). Examples thereof include a group in which a part or all of the group is substituted with a monovalent heteroatom-containing group.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group.
An alkenyl group having 1 to 20 carbon atoms such as an ethenyl group, a propenyl group, and a butenyl group,
A chain hydrocarbon group having 1 to 20 carbon atoms, such as an alkynyl group such as an ethynyl group, a propynyl group, or a butynyl group,
Cycloalkyl groups having 1 to 20 carbon atoms, such as cyclopentyl groups and cyclohexyl groups,
Cycloalkenyl groups having 1 to 20 carbon atoms, such as cyclopropenyl group, cyclopentenyl group, cyclohexenyl group, etc.
Alicyclic hydrocarbon groups having 1 to 20 carbon atoms, such as bridging ring hydrocarbon groups such as norbornyl group and adamantyl group,
Aryl groups having 1 to 20 carbon atoms such as phenyl group, tolyl group, xsilyl group and naphthyl group,
Aralkyl groups having 1 to 20 carbon atoms such as benzyl group, phenethyl group and naphthylmethyl group,
Examples thereof include a group having an aromatic hydrocarbon group having 1 to 20 carbon atoms such as a styryl group, a styrylmethyl group, a vinylbenzyl group, an acenaphthyl group and an acenaphthylmethyl group.

Examples of the divalent heteroatom-containing group include -CO-, -CS-, -NH-, -O-, -S-, and a group combining these. Of these, -O- is preferred, ^{and at least one of R 2} , R ³ , R ⁴ and R ⁵ preferably has an -O- bond.

Examples of the group (α) containing a divalent heteroatom-containing group between carbon-carbon of the hydrocarbon group or between the hydrocarbon group and ^{the carbon atom to which R 2} , R ³ , R ⁴ and R ^{5 are bonded include, for example.} Heteroatom-containing chain groups such as oxoalkyl groups, thioalkyl groups, alkylaminoalkyl groups, alkoxyalkyl groups, alkylthioalkyl groups, alkoxy groups, alkenyloxy groups, and alkynyloxy groups,
Heteroatom-containing cyclic groups such as oxocycloalkyl groups, thiocycloalkyl groups, azacycloalkyl groups, oxacycloalkyl groups, thiacycloalkyl groups, oxocycloalkenyl groups, and oxathiacycloalkyl groups,
Examples thereof include aromatic heterocyclic groups such as heteroaryl groups such as pyrrolyl group, pyridyl group, quinolyl group, isoquinolyl group, furyl group, pyranyl group, thienyl group and benzothiophenyl group.

Examples of the monovalent heteroatom-containing group include a hydroxy group, a sulfanyl group, a cyano group, a nitro group, a halogen atom and the like.

As R ¹ , R ¹⁰ , R ² , R ³ , R ⁴ and R ⁵ , it is preferable that at least one of these is a group containing a crosslinkable group. The "crosslinkable group" is a group capable of forming a covalent bond between molecules by, for example, an addition reaction or a condensation reaction. Since the compound (A) has a crosslinkable group, the compounds (A) and the like are bonded to each other to increase the strength of the resist underlayer film and suppress the sublimation inhibitory property of the resist underlayer film at high temperature during heating. Can be done.

Examples of the crosslinkable group include a carbon-carbon triple bond-containing group, a carbon-carbon double bond-containing group, a hydroxy chain hydrocarbon group, an epoxy group, an alkoxymethyl group, a dialkylaminomethyl group, and a dimethylolaminomethyl group. , Cyanalkyl groups and the like. Among these, a carbon-carbon triple bond-containing group, a carbon-carbon double bond-containing group, a hydroxy chain hydrocarbon group, an acyl group, and a carbonyloxy hydrocarbon group are preferable. As the crosslinkable group, a carbon-carbon triple bond-containing group and a carbon-carbon double bond-containing group are more preferable. At this time, an intermolecular bond can be formed by an addition reaction between carbon-carbon multiple bonds, and as a result, it can be cured without requiring desorption of groups, so that a resist underlayer film is formed while suppressing film shrinkage. As a result, a resist underlayer film having better flatness can be formed.

Examples of the carbon-carbon triple bond-containing group include an ethynyl group, an ethynyloxy group, a propargyl group, a propargyloxy group, a butynyl group, and a butynyloxy group. Examples of the carbon-carbon double bond-containing group include (meth) acryloyl group, (meth) acryloyloxy group, ethenyl group, ethenyloxy group, propenyl group, propenyloxy group, styryl group, styryloxy group, and styrylmethyl group. Examples thereof include a styrylmethyloxy group, a vinylbenzyl group, a vinylbenzyloxy group, an acenaphthylenyl group, an acenaphthylenyloxy group, an acenaphthylenylmethyl group, and an acenaphthylenylmethyloxy group.

Examples of the group containing a crosslinkable group include a group in which a part of hydrogen atoms of a hydrocarbon group such as an aryl group is replaced with the crosslinkable group in addition to the crosslinkable group. As the group containing the crosslinkable group, an ethynyloxy group, a propenyloxy group, a propargyloxy group, a vinylbenzyloxy group, a vinylbenzyloxy group, a 1-propargyloxy group, and a 3-ethynyloxyphenyl group are preferable.

The method for producing the compound (A) is, for example, regarding the following compound (1') in the ^{above formula (1) when R 10} is a hydrogen atom and R ² , R ³ , R ⁴ and R ^{5 are OH.} Can synthesize compound (A) easily and in good yield, for example, according to the following reaction scheme. Further, in the above formula (1), the compound represented by the following formula (1 ″) in the case where ^{R 10} is a hydrogen atom and R ² , R ³ , R ⁴ and R ^{5 are OR ′ is used.} For example, compound (A) can be easily synthesized with good yield according to the following reaction scheme. In the following reaction scheme, the compound (A) is an aldehyde compound represented by the following formula (b) (hereinafter, also referred to as “compound (a)”) as opposed to the compound represented by the following formula (a). , "Compound (b)") can be synthesized by reacting with this solvent in a solvent such as ethanol in the presence of a blended acid catalyst such as hydrochloric acid having a mass ratio of about 2: 1. Next, the compound (A) can be easily synthesized in good yield by reacting with a compound represented by the following formula (d) (hereinafter, also referred to as “compound (d)”).

In the above formula (1 ') and (1'^'), R 1, n1, n2, n3 and n4 are as defined in the above formula (1). R'is an independently monovalent organic group having 1 to 20 carbon atoms. X is a halogen atom.

By following the above reaction scheme, compound (A) can be synthesized easily and in good yield, but a compound having a repeating unit represented by the following formula (2) is also synthesized as a by-product. It is preferable that the by-product is suppressed in the synthesis process or separated and removed by a reprecipitation separation method or the like.

In the above equation (2), x is an integer of 2 or more. R ¹ is synonymous with the above equation (1). R'is an independently monovalent organic group having 1 to 20 carbon atoms. X is a halogen atom.

Examples of the compound (b) include compounds represented by the following formulas.

Examples of the R'include groups represented by the following formulas (3), (4), (5), (6), (8) and (9).

In the above formula (3), R ⁹ is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms. In the above formulas (3), (4), (5), (6), (8) and (9), * indicates a site that binds to X in the above formula (d).

Further, in the method for producing the compound (A), for example, in the above formula (1), R ¹ and R ¹⁰ are monovalent organic groups having 1 to 30 carbon atoms, and R ² , R ³ , R ⁴ and R. ^{Regarding the compound represented by the following formula (1''') when 5} is OH, for example, in the above reaction scheme, instead of the compound (b), the compound represented by the following formula (e) ( Hereinafter, a compound (also referred to as “compound (e)”) is used, and the compound is reacted in the presence of a Lewis acid catalyst such as boron trifluoride-ethyl ether complex or aluminum chloride (III) instead of the blended acid catalyst. (A) can be easily synthesized with good yield.

In the above formula (1 ″'), R ¹ and R ¹⁰ are synonymous with the above formula (1).

Examples of the compound (e) include a compound represented by the following formula (7). Y is a halogen atom.

Examples of the compound (A) include compounds represented by the following formulas (A-1) to (A-14) (hereinafter, also referred to as “compounds (A-1) to (A-14)”). ..

The ratio (A1 / Aa) of the peak area (A1) of the peak containing the compound (A) to the total peak area (Aa) measured by gel permeation chromatography (GPC) analysis of the resist underlayer film forming composition. ) Is 0.25, preferably 0.30, more preferably 0.40, more preferably 0.50, and particularly preferably 0.60.

The value of the ratio (A1 / Aa) can be obtained as follows.
FIG. 2 is a graph of the elution curve measured by gel permeation chromatography (GPC).
(1) In the GPC elution curve 3, the total peak area (Aa) from the retention times c to e and the peak area (A1) of the peak A including the compound (A) are calculated.
By overlapping the hem of the peak A and the hem of the peak B adjacent to the peak A, the detection intensity of the lowest V, which is the lowest detection intensity between the peak top of the peak A and the peak top of the peak B, is determined. When it is higher than the baseline 4, the peak area (A1) is calculated with the holding time d of the lowermost portion V as a boundary. That is, the peak area (A1) is the area from the holding time d to e.
(2) The ratio (A1 / Aa) is calculated from the total peak area (Aa) obtained above and the peak area (A1) of the peak containing the compound (A).

The lower limit of the content ratio of the compound (A) with respect to the peak component containing the compound (A) is preferably 90% by mass, more preferably 95% by mass, and even more preferably 99% by mass. When the content ratio of the compound (A) to the peak component containing the compound (A) is within the above range, the heat resistance, flatness, solvent resistance and etching resistance of the resist underlayer film forming composition can be further enhanced. it can.

The lower limit of the molecular weight of the compound [A] is preferably 400, more preferably 500, and even more preferably 550. As the upper limit of the molecular weight, 1500 is preferable, 1000 is more preferable, and 900 is further preferable.

<[B] Solvent>
The solvent [B] is not particularly limited as long as it can dissolve or disperse the compound [A] and any component contained if necessary.

Examples of the solvent [B] include alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents and the like. [B] The solvent may be used alone or in combination of two or more.

Examples of alcohol-based solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, and the like. sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol , Se-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol , Methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, monoalcohol-based solvents such as cresol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene Glycol, 2,4-pentandiol, 2-methyl-2,4-pentandiol, 2,5-hexanediol, 2,4-heptandiol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol , Polyhydric alcohol-based solvents such as triethylene glycol, tripropylene glycol, and glycerin.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-. Examples thereof include hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentandione, acetonylacetone, diacetone alcohol, acetophenone and fenchone.

Examples of the ether-based solvent include ethyl ether, iso-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, and the like. 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2- (2-ethylbutoxy) ethanol, ethylene glycol dibutyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, 1-n -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl Examples thereof include ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran and the like.

Examples of the ester solvent include diethyl carbonate, methyl acetate, ethyl acetate, amyl γ-butyrolactone acetate, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-acetate. Butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetate , Acetate ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso propionate -Amil, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like can be mentioned.

Examples of the nitrogen-containing solvent include N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, and N-methyl. Pyrrolidone and the like can be mentioned.

Among these, ether-based solvents and ester-based solvents are preferable, and ether-based solvents and ester-based solvents having a glycol structure are more preferable from the viewpoint of excellent film-forming properties, and propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol. Monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl acetate monopropyl ether are more preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

[B] The lower limit of the content of the ether solvent and the ester solvent having a glycol structure in the solvent is preferably 20% by mass, more preferably 60% by mass, further preferably 90% by mass, and particularly preferably 100% by mass. preferable.

<[C] Acid generator>
The [C] acid generator is a component that generates an acid by the action of heat or light and promotes the cross-linking of the [A] compound. When the resist underlayer film forming composition contains the [C] acid generator, the cross-linking reaction of the [A] compound is promoted, and the hardness of the formed film can be further increased. [C] The acid generator can be used alone or in combination of two or more.

[C] Examples of the acid generator include onium salt compounds and N-sulfonyloxyimide compounds.

Examples of the onium salt compound include a sulfonium salt, a tetrahydrothiophenium salt, an iodonium salt, an ammonium salt and the like.

Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, and triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2. -Tetrafluoroethane sulfonate, 4-cyclohexylphenyldiphenyl sulfonium trifluoromethane sulfonate and the like can be mentioned.

Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium nona. Fluoro-n-butane sulfonate, 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetra Fluoroethane sulfonate and the like can be mentioned.

Examples of the iodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butane sulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butane sulfonate, and bis (4-t-butylphenyl) iodonium. Examples thereof include 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate.

Examples of the ammonium salt include triethylammonium trifluoromethanesulfonate, triethylammonium nonafluoro-n-butane sulfonate and the like.

Examples of the N-sulfonyloxyimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and N- (nonafluoro-n-butanesulfonyloxy). ) Bicyclo [2.2.1] hept-5-en-2,3-dicarboxyimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2- Tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and the like can be mentioned.

Among these, as the [C] acid generator, an onium salt compound is preferable, an iodonium salt and an ammonium salt are more preferable, and bis (4-t-butylphenyl) iodonium nonafluoro-n-butane sulfonate and triethylammonium nona are used. Fluoro-n-butane sulfonate is more preferred.

When the resist underlayer film forming composition contains the [C] acid generator, the lower limit of the content of the [C] acid generator is 0.1 part by mass with respect to 100 parts by mass of the [A] compound. Is preferable, 1 part by mass is more preferable, and 3 parts by mass is further preferable. The upper limit of the content is preferably 15 parts by mass, more preferably 12 parts by mass, and even more preferably 10 parts by mass. By setting the content of the [C] acid generator in the above range, the cross-linking reaction of the [A] compound can be promoted more effectively.

[[D] Crosslinking agent]
The [D] cross-linking agent is a component that forms a cross-linking bond between the compounds contained in the [A] compound in the resist underlayer film forming composition by the action of heat or acid, or forms a cross-linking structure by itself. Is. When the resist underlayer film forming composition contains the [D] cross-linking agent, the hardness of the resist underlayer film to be formed can be increased. [D] The cross-linking agent may be used alone or in combination of two or more.

[D] Examples of the cross-linking agent include a polyfunctional (meth) acrylate compound, an epoxy compound, a hydroxymethyl group-substituted phenol compound, an alkoxyalkyl group-containing phenol compound, a compound having an alkoxyalkylated amino group, and the following formula (11-). Examples thereof include a random copolymer of acenaphthylene represented by P) and hydroxymethyl acenaphthylene, and compounds represented by the following formulas (11-1) to (11-12).

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropantri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta. (Meta) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Examples thereof include (meth) acrylate, dipropylene glycol di (meth) acrylate, and bis (2-hydroxyethyl) isocyanurate di (meth) acrylate.

Examples of the epoxy compound include novolak type epoxy resin, bisphenol type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and the like.

Examples of the hydroxymethyl group-substituted phenol compound include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, and 3,5-dihydroxymethyl-4-methoxytoluene [2,6-]. Bis (hydroxymethyl) -p-cresol] and the like.

Examples of the alkoxyalkyl group-containing phenol compound include a methoxymethyl group-containing phenol compound and an ethoxymethyl group-containing phenol compound.

Examples of the compound having an alkoxyalkylated amino group include, for example, (poly) methylolated melamine, (poly) methylolated glycoluryl, (poly) methylolated benzoguanamine, (poly) methylolated urea, and the like in one molecule. Examples thereof include a nitrogen-containing compound having an active methylol group in which at least one hydrogen atom of the hydroxyl group of the methylol group is substituted with an alkyl group such as a methyl group or a butyl group. The compound having an alkoxyalkylated amino group may be a mixture of a plurality of substituted compounds, or may contain an oligomer component partially self-condensed.

In the above formulas (11-6), (11-8), (11-11) and (11-12), Me represents a methyl group, Et represents an ethyl group, and Ac represents an acetyl group.

The compounds represented by the above formulas (11-1) to (11-12) can be synthesized with reference to the following documents.
(1) Compound represented by the formula (11-1) Guo, Qun-Sheng; Lu, Young-Na; Liu, Bing; Xiao, Jian; Li, Jin-Shan Journal of Organometallic Chemistry, 2006, vol. 691, # 6 p. 1282-1287
(2) Compound represented by the formula (11-2) Badar, Y. et al. et al. Journal of the Chemical Society, 1965, p. 1412-1418
(3) Compounds represented by the formula (11-3) Hsieh, Jen-Chieh; Cheng, Cheen-Hong Chemical Communications (Cambridge, United Kingdom), 2008, # 26 p. 2992-2994
(4) Compound represented by formula (11-4) Compound represented by formula (11-5) of JP-A-5-238990. Bacon, R. et al. G. R. Bankhead, R.M. Journal of the Chemical Society, 1963, p. 839-845
(6) Compounds represented by formulas (11-6), (11-8), (11-11) and (11-12) Macromolecules 2010, vol. 43, p2832-2839
(7) Compounds represented by formulas (11-7), (11-9) and (11-10) Polymer Journal 2008, vol. 40, No. 7, p645-650, and Journal of Polymer Science: Part A, Polymer Chemistry, Vol. 46, p4949-4955

Among these [D] cross-linking agents, methoxymethyl group-containing phenol compounds, compounds having an alkoxyalkylated amino group, and random copolymers of acenaphthylene and hydroxymethyl acenaphthylene are preferable, and they are alkoxyalkylated. Compounds having an amino group are more preferable, and 1,3,4,6-tetra (methoxymethyl) glycoluryl is even more preferable.

When the resist underlayer film forming composition contains a [D] cross-linking agent, the lower limit of the content of the [D] cross-linking agent is preferably 0.1 part by mass with respect to 100 parts by mass of the [A] compound. , 0.5 parts by mass is more preferable, 1 part by mass is further preferable, and 3 parts by mass is particularly preferable. The upper limit of the content is preferably 50 parts by mass, more preferably 40 parts by mass, further preferably 30 parts by mass, and particularly preferably 20 parts by mass. By setting the content of the [D] cross-linking agent in the above range, the cross-linking reaction of the [A] compound can be more effectively caused.

<Other optional ingredients>
Examples of other optional components include surfactants and the like.

[Surfactant]
The composition for forming a resist underlayer film can improve the coatability by containing a surfactant, and as a result, the uniformity of the coated surface of the resist underlayer film to be formed is improved and the coating spots are formed. Can be suppressed. The surfactant may be used alone or in combination of two or more.

When the resist underlayer film forming composition contains a surfactant, the lower limit of the content of the surfactant is preferably 0.01 part by mass and 0.05 parts by mass with respect to 100 parts by mass of the compound [A]. By mass is more preferred, and 0.1 parts by mass is even more preferred. As the upper limit of the content, 10 parts by mass is preferable, 5 parts by mass is more preferable, and 1 part by mass is further preferable. By setting the content of the surfactant in the above range, the coatability of the resist underlayer film forming composition can be further improved.

[Method for preparing composition for forming resist underlayer film]
The resist underlayer film forming composition is obtained by mixing [A] compound, [B] solvent,, if necessary, [C] acid generator, [D] cross-linking agent, and other optional components in a predetermined ratio. , Preferably, the obtained mixture can be prepared by filtering with a membrane filter of about 0.1 μm or the like. The lower limit of the solid content concentration of the resist underlayer film forming composition is preferably 0.1% by mass, more preferably 1% by mass, further preferably 3% by mass, and particularly preferably 5% by mass. The upper limit of the solid content concentration is preferably 50% by mass, more preferably 30% by mass, further preferably 20% by mass, and particularly preferably 15% by mass. For the solid content concentration, 0.5 g of the resist underlayer film forming composition was fired at 250 ° C. for 30 minutes to measure the mass of the solid content with respect to 0.5 g of the resist underlayer film forming composition, and the resist underlayer film was formed. The solid content concentration (mass%) of the composition for use was calculated.

Since the resist underlayer film forming composition can form a resist underlayer film having excellent flatness and excellent solvent resistance, etching resistance and heat resistance, it is necessary to form a resist underlayer film in the manufacture of semiconductor devices and the like. Can be suitably used for.

<Resist underlayer film>
The resist underlayer film of the present invention is formed from the resist underlayer film forming composition. Since the resist underlayer film is formed from the above-mentioned resist underlayer film forming composition, it is excellent in flatness and excellent in solvent resistance, etching resistance and heat resistance.

<Method of forming resist underlayer film>
The method for forming the resist underlayer film is a step of applying the above-mentioned resist underlayer film forming composition on at least one surface side of the substrate (hereinafter, also referred to as “coating step”) and the above coating step. It includes a step of heating the coating film to be formed (hereinafter, also referred to as a “heating step”). According to the method for forming a resist underlayer film, since the above-mentioned composition for forming a resist underlayer film is used, it is possible to form a resist underlayer film having excellent flatness and excellent solvent resistance, etching resistance and heat resistance.

[Coating process]
In this step, the resist underlayer film forming composition is applied to at least one surface side of the substrate.

Examples of the substrate include silicon wafers and wafers coated with aluminum. Further, the coating method of the resist underlayer film forming composition is not particularly limited, and can be carried out by an appropriate method such as rotary coating, casting coating, roll coating, etc., whereby the coating film can be applied. Can be formed.

[Heating process]
In this step, the coating film formed by the above coating process is heated. As a result, a resist underlayer film is formed.

The heating of the resist underlayer film is usually performed in the atmosphere. As the lower limit of the heating temperature, 150 ° C. is preferable, 200 ° C. is more preferable, and 250 ° C. is further preferable. The upper limit of the heating temperature is preferably 500 ° C., more preferably 450 ° C., and even more preferably 420 ° C. When the heating temperature range is in the above range, the oxidative cross-linking can proceed satisfactorily and the properties required for the resist film can be exhibited. The lower limit of the heating time is preferably 15 seconds, more preferably 30 seconds, and even more preferably 45 seconds. The upper limit of the heating time is preferably 1,200 seconds, more preferably 600 seconds, and even more preferably 300 seconds.

Before heating the resist underlayer film at a temperature of 150 ° C. or higher and 500 ° C. or lower, preheating may be performed at a temperature of 60 ° C. or higher and 250 ° C. or lower. As the lower limit of the heating time in the preheating, 10 seconds is preferable, and 30 seconds is more preferable. The upper limit of the heating time is preferably 300 seconds, more preferably 180 seconds. By performing this preheating, the solvent is vaporized in advance to make the resist underlayer film dense, so that the dehydrogenation reaction that occurs during the subsequent heating can be efficiently promoted.

In the method for forming the resist underlayer film, the resist underlayer film is heated to form the resist underlayer film, but the resist underlayer film forming composition contains the [C] acid generator, and [C] When the acid generator is a radiation-sensitive acid generator, the resist underlayer film can be cured to form the resist underlayer film by combining exposure and heating. The radiation used for this exposure includes electromagnetic waves such as visible light, ultraviolet rays, far ultraviolet rays, X-rays and γ-rays, and particle beams such as electron beams, molecular beams and ion beams, depending on the type of [C] acid generator. It is selected as appropriate.

The lower limit of the average thickness of the resist underlayer film to be formed is preferably 50 nm, more preferably 100 nm, and even more preferably 180 nm. The upper limit of the average thickness is preferably 3,000 nm, more preferably 2,000 nm, and even more preferably 500 nm.

<Manufacturing method of patterned substrate>
The method for manufacturing the patterned substrate is also referred to as a step of forming a resist pattern on the surface side of the resist underlayer film formed by the method for forming the resist underlayer film, which is opposite to the substrate (hereinafter, also referred to as a "resist pattern forming step"). It is provided with a step of performing etching using the resist pattern as a mask (hereinafter, also referred to as an “etching step”).

As a method for producing the patterned substrate, a resist underlayer film formed by the method for forming the resist underlayer film is used. Since the resist underlayer film is excellent in flatness and excellent in solvent resistance, etching resistance and heat resistance, it is possible to obtain a patterned substrate having an excellent pattern shape according to the method for producing the patterned substrate. it can.

The method for manufacturing the patterned substrate includes, if necessary, a step of forming an intermediate layer (intermediate film) on the surface side of the resist underlayer film opposite to the substrate before the resist pattern forming step. You may be. Hereinafter, each step will be described.

[Intermediate layer forming process]
In this step, an intermediate layer is formed on the surface side of the resist underlayer film opposite to the substrate. This intermediate layer is a layer to which the above-mentioned functions are added in order to further supplement the functions of the resist underlayer film and / or the resist film in the formation of the resist pattern, or to give the functions that they do not have. .. For example, when the antireflection film is formed as an intermediate layer, the antireflection function of the resist underlayer film can be further supplemented.

This intermediate layer can be formed of an organic compound or an inorganic oxide. Examples of the above-mentioned organic compounds include commercially available products such as "DUV-42", "DUV-44", "ARC-28" and "ARC-29" manufactured by Brewer Science, and "AR-3" manufactured by Roam and Haas. , "AR-19" and the like. Examples of the commercially available inorganic oxide include JSR's "NFC SOG01", "NFC SOG04", and "NFC SOG080". Further, as the inorganic oxide, polysiloxane, titanium oxide, aluminum oxide, tungsten oxide and the like formed by the CVD method can be used.

The method for forming the intermediate layer is not particularly limited, but for example, a coating method, a CVD method, or the like can be used. The average thickness of the intermediate layer is appropriately selected according to the function required for the intermediate layer, but the lower limit of the average thickness of the intermediate layer is preferably 10 nm, more preferably 20 nm. The upper limit of the average thickness is preferably 3,000 nm, more preferably 300 nm.

[Resist pattern forming process]
In this step, a resist pattern is formed on the surface side of the resist underlayer film opposite to the substrate. When the intermediate layer forming step is performed, a resist pattern is formed on the upper surface side of the intermediate layer. Examples of the method for performing this step include a method using a resist composition and the like.

In the method using the resist composition, specifically, the resist composition is applied so that the obtained resist film has a predetermined thickness, and then the solvent in the coating film is volatilized by prebaking. , Form a resist film.

Examples of the resist composition include a positive-type or negative-type chemically amplified resist composition containing a radiation-sensitive acid generator, a positive-type resist composition containing an alkali-soluble resin and a quinonediazide-based photosensitive agent, and an alkali-soluble. Examples thereof include a negative resist composition containing a resin and a cross-linking agent.

The lower limit of the solid content concentration of the resist composition is preferably 0.3% by mass, more preferably 1% by mass. The upper limit of the solid content concentration is preferably 50% by mass, more preferably 30% by mass. Further, the resist composition is generally filtered through, for example, a filter having a pore size of about 0.2 μm to be used for forming a resist film. In this step, a commercially available resist composition can be used as it is.

The method for applying the resist composition is not particularly limited, and examples thereof include a spin coating method. The prebake temperature is appropriately adjusted according to the type of resist composition used and the like, but the lower limit of the temperature is preferably 30 ° C., more preferably 50 ° C. The upper limit of the temperature is preferably 200 ° C., more preferably 150 ° C. As the lower limit of the prebaking time, 10 seconds is preferable, and 30 seconds is more preferable. The upper limit of the time is preferably 600 seconds, more preferably 300 seconds.

Next, the resist film formed above is exposed by selective irradiation. The radiation used for exposure includes electromagnetic waves such as visible light, ultraviolet rays, far ultraviolet rays, X-rays, and γ-rays, and electron beams and molecular beams, depending on the type of radiation-sensitive acid generator used in the resist composition. Appropriately selected from particle beams such as ion beams. Among these, deep ultraviolet rays are preferable, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), _{F 2} excimer laser light (wavelength 157 nm), Kr ₂ excimer laser light (wavelength 147 nm), ArKr excimer laser beam (Radiation 134 nm) and extreme ultraviolet (UVV such as wavelength 13.5 nm) are more preferable, and KrF excimer laser light, ArF excimer laser light and EUV are further preferable. After the above exposure, post-baking can be performed to improve the resolution, pattern profile, developability, and the like.

Next, the exposed resist film is developed with a developing solution to form a resist pattern. This development may be alkaline development or organic solvent development. As the developing solution, in the case of alkaline development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [ 4.3.0] Examples thereof include an alkaline aqueous solution in which at least one alkaline compound such as -5-nonene is dissolved. An appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol, a surfactant and the like can be added to these alkaline aqueous solutions. Further, in the case of organic solvent development, examples of the developing solution include various organic solvents exemplified as the [B] solvent of the above-mentioned resist underlayer film forming composition, and more specifically, n-butyl acetate. Examples thereof include iso-butyl acetate, sec-butyl acetate and amyl acetate. A predetermined resist pattern is formed by washing and drying after development with the above developer.

As a method for performing the resist pattern forming step, in addition to the method using the above-mentioned resist composition, a method using a nanoimprint method, a method using a self-assembling composition, and the like can also be used.

[Etching process]
In this step, etching is performed using the resist pattern as a mask. As a result, a pattern is formed on the substrate. The number of times of etching may be once or a plurality of times, that is, the pattern obtained by etching may be used as a mask for sequential etching, but from the viewpoint of obtaining a pattern having a better shape, a plurality of times is preferable. When the etching is performed a plurality of times, if the intermediate layer is not provided, the resist underlayer film and the substrate are sequentially etched, and if the intermediate layer is provided, the intermediate layer, the resist underlayer film, and the substrate are sequentially etched. Examples of the etching method include dry etching and wet etching. Among these, dry etching is preferable from the viewpoint of improving the shape of the pattern on the substrate. For this dry etching, for example, gas plasma such as oxygen plasma is used. After the etching, a patterned substrate having a predetermined pattern is obtained.

<Compound>
The compound is a compound represented by the above formula (1). Since the compound has the above-mentioned properties, it can be suitably used as a component of the composition for forming a resist underlayer film.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The measurement method of various physical property values is shown below.

[Mw and content ratio]
For the polystyrene-equivalent weight average molecular weight (Mw) of the resist underlayer film forming composition, a GPC column (2 "G2000HXL" and 1 "G3000HXL") manufactured by Toso Co., Ltd. was used, and the flow rate: 1.0 mL / min, elution solvent: It was measured by gel permeation chromatography (detector: differential refractometer (RI), light source wavelength of differential refractometer: 658 nm) using monodisperse polystyrene as a standard under analytical conditions of tetrahydrofuran and column temperature: 40 ° C.

[Average thickness of film]
The average thickness of the membrane was measured using a spectroscopic ellipsometer (“M2000D” from JA WOOLLAM).

<Synthesis of [A] compound>
The compounds represented by the following formulas (A-1) to (A-14) were synthesized by the procedure shown below.

[Example 1-1] (Synthesis of compound (A-1))
In a three-necked flask equipped with a thermometer, a condenser and a magnetic stirrer, 20 g (91.6 mmol) of 1-hydroxypyrene, 6.61 g (55.0 mmol) of o-tolualdehyde and 60 g of ethanol were charged under a nitrogen atmosphere, and the temperature was changed to room temperature. It was dissolved in. After cooling to 5 ° C., 40 g of a 35% aqueous hydrochloric acid solution was added dropwise over 30 minutes. After completion of the dropping, the mixture was heated to 60 ° C. and reacted for 10 hours. After completion of the reaction, the reaction solution was added to a large amount of water, and then 60 g of methyl isobutyl ketone (MIBK) and 30 g of THF were added for extraction. After washing with water three times, the organic phase was put into 600 g of hexane and reprecipitated. The precipitate was dried under reduced pressure at 60 ° C. overnight to obtain 22.6 g of a reaction product (P1) containing the above compound (A-1).

[Example 1-2] (Synthesis of compound (A-2))
10 g of reaction product (P1) containing the above compound (A-1) obtained in Example 1-1 and 40 g of N, N-dimethylacetamide in a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer. And 5.65 g (40.8 mmol) of potassium carbonate was charged under nitrogen. Next, the mixture was heated to 80 ° C., 4.86 g (40.8 mmol) of propargyl bromide was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-2). 12.1 g of product (P2) was obtained.

[Example 1-3] (Synthesis of compound (A-3))
The above compound (A-3) was obtained in the same manner as in Example (1-2) except that 4.86 g (40.8 mmol) of propargyl bromide was changed to 6.23 g (40.8 mmol) of 4- (chloromethyl) styrene. 13.2 g of the reaction product (P3) containing the above was obtained.

[Example 1-4] (Synthesis of compound (A-4))
Reaction formation containing the above compound (A-4) in the same manner as in Example (1-2) except that 4.86 g (40.8 mmol) of propargyl bromide was changed to 4.94 g (40.8 mmol) of allyl bromide. A product (P4) of 10.1 g was obtained.

[Example 1-5] (Synthesis of compound (A-5))
The following compound (a-1) is contained in the same manner as in Example (1-1) except that 6.61 g (55.0 mmol) of o-tolvaldehyde is changed to 8.59 g (55.0 mmol) of 1-naphthaldehyde. 20.5 g of the reaction product (p1) was obtained.

5. In a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer, 10.9 g of the obtained reaction product (p1) containing the above compound (a-1), 40 g of N, N-dimethylacetamide and potassium carbonate. 65 g (40.8 mmol) was charged under nitrogen. Next, the mixture was heated to 80 ° C., 4.86 g (40.8 mmol) of propargyl bromide was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-5). 12.5 g of product (P5) was obtained.

[Example 1-6] (Synthesis of compound (A-6))
The following compound (a-2) was obtained in the same manner as in [Example 1-1] except that 6.61 g (55.0 mmol) of o-tolvaldehyde was changed to 10.02 g (55.0 mmol) of biphenyl-4-carboxyaldehyde. ) Contained 24.2 g of the reaction product (p2).

4. 11.2 g of the obtained reaction product (p2) containing the above compound (a-2), 40 g of N, N-dimethylacetamide and potassium carbonate in a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer. 65 g (40.8 mmol) was charged under nitrogen. Next, the mixture was heated to 80 ° C., 4.86 g (40.8 mmol) of propargyl bromide was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-6). 12.0 g of product (P6) was obtained.

[Example 1-7] (Synthesis of compound (A-7))
20 g (91.6 mmol) of 1-hydroxypyrene, 6.61 g (55.0 mmol) of o-tolvaldehyde, 21.28 g (91.6 mmol) of 1-methoxypyrene, 7.59 g (55.0 mmol) of 2,4-dihydroxybenzaldehyde. In the same manner as in [Example 1-1], 24.2 g of a reaction product (p3) containing the following compound (a-3) was obtained.

5. In a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer, 10.9 g of the obtained reaction product (p3) containing the above compound (a-3), 40 g of N, N-dimethylacetamide and potassium carbonate. 65 g (40.8 mmol) was charged under nitrogen. Next, the mixture was heated to 80 ° C., 4.86 g (40.8 mmol) of propargyl bromide was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-7). 12.2 g of product (P7) was obtained.

[Example 1-8] (Synthesis of compound (A-8))
In a three-necked flask equipped with a thermometer, a condenser and a magnetic stirrer, 20 g (91.6 mmol) of 1-hydroxypyrene and 11.95 g of 1,2-dichloroethane were charged under a nitrogen atmosphere and dissolved at 80 ° C. After dissolution, 11.96 g (50.4 mmol) of α, α-dichlorodiphenylmethane and 26.0 g (183 mmol) of boron trifluoride-ethyl ether complex were added, and the mixture was reacted at 80 ° C. for 10 hours. After completion of the reaction, the reaction solution was washed with a large amount of water three times, and then the organic phase was put into 600 g of hexane and reprecipitated. The precipitate was dried under reduced pressure at 60 ° C. overnight to obtain 19.6 g of the reaction product (p4) containing the compound (a-4) below.

4. 11.2 g of the obtained reaction product (p4) containing the above compound (a-4), 40 g of N, N-dimethylacetamide and potassium carbonate in a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer. 65 g (40.8 mmol) was charged under nitrogen. Next, the mixture was heated to 80 ° C., 6.23 g (40.8 mmol) of 4- (chloromethyl) styrene was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-8). 13.6 g of product (P8) was obtained.

[Example 1-9] (Synthesis of compound (A-9))
The above compound (A-9) is contained in the same manner as in Example (1-5) except that the amount of 1-naphthaldehyde added is changed from 8.59 g (55.0 mmol) to 11.2 g (71.5 mmol). 22.4 g of the reaction product (P9) was obtained.

[Example 1-10] (Synthesis of compound (A-10))
10 g of the reaction product (P9) containing the compound (A-9) obtained in Example 1-9 above, 40 g of N, N-dimethylacetamide and 40 g of the reaction product (P9) in a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer. 5.65 g (40.8 mmol) of potassium carbonate was charged under nitrogen. Next, the mixture was heated to 80 ° C., 4.86 g (40.8 mmol) of propargyl bromide was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-10). 12.8 g of product (P10) was obtained.

[Example 1-11] (Synthesis of compound (A-11))
A reaction product containing the following compound (a-5) in the same manner as in Example (1-1) except that 6.61 g (55.0 mmol) of o-tolaldehyde was changed to 6.28 g (55.0 mmol) of pentanal. (P5) 19.8 g was obtained.

5. In a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer, 9.57 g of the obtained reaction product (p5) containing the above compound (a-5), 40 g of N, N-dimethylacetamide and potassium carbonate. 65 g (40.8 mmol) was charged under nitrogen. Next, the mixture was heated to 80 ° C., 4.86 g (40.8 mmol) of propargyl bromide was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-11). 10.6 g of product (P11) was obtained.

[Example 1-12] (Synthesis of compound (A-12))
Reaction product containing the following compound (a-6) in the same manner as in Example (1-1) except that 6.61 g (55.0 mmol) of o-tolvaldehyde was changed to 10.1 g (55.0 mmol) of dodecanal. (P6) 22.5 g was obtained.

4. In a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer, 11.4 g of the obtained reaction product (p6) containing the above compound (a-6), 40 g of N, N-dimethylacetamide and potassium carbonate. 65 g (40.8 mmol) was charged under nitrogen. Next, the mixture was heated to 80 ° C., 4.86 g (40.8 mmol) of propargyl bromide was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-12). 12.3 g of product (P12) was obtained.

[Example 1-13] (Synthesis of compound (A-13))
The following compound (a-7) was prepared in the same manner as in Example (1-1) except that 6.61 g (55.0 mmol) of o-tolvaldehyde was changed to 7.05 g (55.0 mmol) of 2-propyloctanal. 20.1 g of the containing reaction product (p7) was obtained.

4. 11.1 g of the obtained reaction product (p6) containing the above compound (a-6), 40 g of N, N-dimethylacetamide and potassium carbonate in a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer. 65 g (40.8 mmol) was charged under nitrogen. Next, the mixture was heated to 80 ° C., 4.86 g (40.8 mmol) of propargyl bromide was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-13). 11.3 g of product (P13) was obtained.

[Example 1-14] (Synthesis of compound (A-14))
The following compound (a-8) was prepared in the same manner as in Example (1-1) except that 6.61 g (55.0 mmol) of o-tolaldehyde was changed to 12.1 g (55.0 mmol) of m-PEG4-aldehyde. 23.9 g of the containing reaction product (p8) was obtained.

4. 12.1 g of the obtained reaction product (p8) containing the above compound (a-8), 40 g of N, N-dimethylacetamide and potassium carbonate in a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer. 65 g (40.8 mmol) was charged under nitrogen. Next, the mixture was heated to 80 ° C., 4.86 g (40.8 mmol) of propargyl bromide was added, and the mixture was stirred for 6 hours to carry out the reaction. Then, 40 g of MIBK and 80 g of water were added to the reaction solution to carry out a liquid separation operation, and then the organic phase was put into a large amount of methanol and the precipitated compound was filtered to contain the above compound (A-14). 11.3 g of product (P14) was obtained.

<Synthesis of comparative compounds (b-1) to (b-3)>
[Synthesis Example 1-1] (Synthesis of compound (b-1))
A reactor equipped with a condenser, a thermometer and a stirrer is charged with 100 g of 2,7-dihydroxynaphthalene, 100 g of propylene glycol monomethyl ether acetate and 50 g of paraformaldehyde, 2 g of oxalic acid is added, and the temperature is raised to 120 ° C. while dehydrating. Then, the reaction was carried out for 5 hours to obtain a compound (b-1) which is a polymer having a structural unit represented by the following formula (b-1).

[Synthesis Example 1-2] (Synthesis of compound (b-2))
In a three-necked flask equipped with a thermometer, condenser and magnetic stirrer, 20 g (91.6 mmol) of 1-hydroxypyrene, 7.16 g (45.8 mmol) of 2-naphtholaldehyde, and propylene glycol monomethyl ether (PGME) under a nitrogen atmosphere. ) 82 g was charged and dissolved at room temperature. After dissolution, 8.81 g (91.6 mmol) of methanesulfonic acid was added, and the mixture was stirred at 120 ° C. for 12 hours for polymerization. After completion of the polymerization, the polymerization reaction solution is put into a large amount of a mixed solution of methanol / water (80/20 vol%), and the precipitated resin is filtered to have a structural unit represented by the following formula (b-2). A polymer compound (b-2) was obtained.

[Synthesis Example 1-3] (Synthesis of compound (b-3))
20 g (91.6 mmol) of 1-hydroxypyrene, 6.30 g (40.3 mmol) of 2-naphtholaldehyde, propylene glycol monomethyl ether acetate in a three-necked flask equipped with a thermometer, condenser and magnetic stirrer under a nitrogen atmosphere. 82 g was charged and dissolved at room temperature. After dissolution, 8.81 g (91.6 mmol) of methanesulfonic acid was added, and the mixture was stirred at 120 ° C. for 12 hours for polymerization. After completion of the polymerization, the polymerization reaction solution is poured into a large amount of methanol, and the precipitated resin is filtered to obtain a compound (b-3) which is a polymer having a structural unit represented by the following formula (b-3). Obtained.

<Preparation of composition for forming a resist underlayer film>
The [B] solvent, [C] acid generator and [D] cross-linking agent used in the preparation of the resist underlayer film forming composition are shown below.

[[B] Solvent]
B-1: Propylene glycol monomethyl ether acetate

[[C] Acid generator]
C-1: Bis (4-t-butylphenyl) iodonium nonafluoro-n-butane sulfonate (compound represented by the following formula (C-1))
C-2: Triethylammonium nonafluoro-n-butane sulfonate (compound represented by the following formula (C-2))

[[D] Crosslinking agent]
D-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluryl (compound represented by the following formula (D-1))
D-2: 4,4'-(1- (4- (1- (1- (4-hydroxy-3,5-bis (methoxymethyl) phenyl) -1-methylethyl) phenyl) ethylidene) bis (2,6- Bis (methoxymethyl) phenol (compound represented by the following formula (D-2))

[Example 2-1]
10 parts by mass of the synthesized reaction product (P1) containing (A-1) was dissolved in 90 parts by mass of (B-1) as the solvent for [B]. The obtained solution was filtered through a membrane filter having a pore size of 0.1 μm to prepare a resist underlayer film forming composition (J-1).

[Examples 2-1 to 2-16 and Comparative Examples 2-1 to 2-3]
The resist underlayer film forming compositions (J-2) to (J-16) and (CJ-1) were operated in the same manner as in Example 1 except that the components of the types and contents shown in Table 1 below were used. )-(CJ-3) were prepared. “-” In Table 1 indicates that the corresponding component was not used, and Mw and A1 / Aa were not analyzed.

<Formation of resist underlayer film>
The above-prepared composition for forming a resist underlayer film was applied onto a silicon wafer substrate by a spin coating method. Next, in an air atmosphere, the resist underlayer film is heated (baked) at the heating temperature (° C.) and the heating time (sec) shown in Table 2 below to form a resist underlayer film having an average thickness of 200 nm, and the resist underlayer film is formed on the substrate. A substrate with a resist underlayer film was obtained.

<Evaluation>
Using the obtained composition for forming a resist underlayer film and the obtained substrate with a resist underlayer film, the following items were evaluated by the following methods. The evaluation results are shown in Table 2 below. “-” In Table 2 indicates that Comparative Example 3-1 is a criterion for evaluating etching resistance.

[Solvent resistance]
The obtained substrate with a resist underlayer film was immersed in cyclohexanone (room temperature) for 1 minute. The average film thickness before and after immersion was measured. _{Let X 0 be} the average thickness of the resist underlayer film before immersion and X be the average thickness of the resist underlayer film after immersion, and calculate the absolute value of the numerical value obtained by _{(XX 0} ) × 100 / X _{0 to calculate the thickness.} The rate of change (%) was used. The solvent resistance is "A" (good) when the film thickness change rate is less than 1%, "B" (slightly good) when the film thickness change rate is 1% or more and less than 5%, and "C" when the film thickness change rate is 5% or more. It was evaluated as (defective).

[Etching resistance]
The resist underlayer film on the obtained substrate with the resist underlayer film was subjected to CF ₄ / Ar = 110/440 sccm, PRESS. = 30 MT, HF RF (high frequency power for plasma generation) = 500 W, LF RF (high frequency power for bias) = 3000 W, DCS = -150 V, RDC (gas center flow ratio) = 50%, 30 sec The etching rate (nm / min) was calculated from the average thickness of the resist underlayer film before and after, and the ratio to Comparative Example 3-1 was calculated and used as a measure of etching resistance. The etching resistance is 1.0 or more, "A" (extremely good) when the above ratio is 0.95 or more and less than 0.98, and "B" (good) when the above ratio is 0.98 or more and less than 1.00. In the case of, it was evaluated as "C" (defective).

[Flatness]
As shown in FIG. 1, the prepared resist underlayer film forming composition is placed on a silicon substrate 1 on which a trench pattern having a depth of 100 nm and a width of 10 μm is formed, and a spin coater (“CLEAN TRACK ACT 12” manufactured by Tokyo Electron Limited”. ) Was used for coating by the spin coating method. The rotation speed of the spin coat was the same as in the case of forming the resist underlayer film having an average thickness of 200 nm in the above-mentioned "formation of the resist underlayer film". Next, in an air atmosphere, the silicon substrate is baked (baked) at 250 ° C. for 60 seconds to form a film 2 having an average thickness of 200 nm in the non-trench pattern portion, and the silicon substrate with a film coated with the film is formed. Obtained.

The cross-sectional shape of the silicon substrate with a film was observed with a scanning electron microscope (“S-4800” manufactured by Hitachi High-Technologies Corporation), and the height of the resist underlayer film at the central portion b of the trench pattern and the trench pattern. The difference (ΔFT) from the height in the non-trench pattern portion a at a position 5 μm from the end was used as an index of flatness. The flatness is "A" (extremely good) when this ΔFT is less than 20 nm, "B" (better) when it is 20 nm or more and less than 30 nm, and "C" (good) when it is 30 nm or more and less than 40 nm. When it was 40 nm or more, it was evaluated as "D" (defective). The difference in height shown in FIG. 1 is exaggerated from the actual height.

[Heat-resistant]
The above-prepared composition for forming a resist underlayer film is applied onto a silicon wafer having a diameter of 8 inches by a spin coating method, and baked at 250 ° C. for 60 seconds in an air atmosphere to form a resist underlayer film. Then, a substrate with a resist underlayer film was obtained. Next, the powder is recovered by scraping the resist underlayer film of the substrate with the resist underlayer film, and the powder of the resist underlayer film is used for measurement by the TG-DTA device (“TG-DTA2000SR” of NETZSCH). And the mass before heating was measured. Next, using a TG-DTA device (“TG-DTA2000SR” manufactured by NETZSCH), the mixture is heated to 400 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere, and the mass of the powder at 400 ° C. is measured. did. Then, the mass reduction rate (%) was measured by the following formula, and this mass reduction rate was used as a measure of heat resistance.
_{M L = {(m1-m2} ) / m1} × 100
Here, in the above formula, _{M L} is a mass reduction rate (%), m1 is the pre-heating the mass (mg), m @ 2 is the mass (mg) at 400 ° C..
The smaller the mass reduction rate of the powder as a sample, the less the sublimation product and the decomposition product of the resist underlayer film generated when the resist underlayer film is heated, and the better the heat resistance. That is, the smaller the mass reduction rate, the higher the heat resistance. The heat resistance is "A" (extremely good) when the mass reduction rate is less than 5%, "B" (good) when the mass reduction rate is 5% or more and less than 10%, and "C" (good) when the mass reduction rate is 10% or more. Defective).

As is clear from the results in Table 2, the resist underlayer film formed from the semiconductor resist underlayer film forming composition of the examples is good in all evaluation items of heat resistance, flatness, solvent resistance and etching resistance. Results were obtained. In particular, in Example 3-2, Example 3-4, Example 3-5, Example 3-6, Example 3-8 and Examples 3-13 to 3-15, all items It was excellent. On the other hand, the resist underlayer film formed from the composition for forming the resist underlayer film for semiconductors of the comparative example was inferior in etching resistance or flatness.

According to the composition for forming a resist underlayer film for semiconductors of the present invention, it is possible to form a resist underlayer film having excellent heat resistance and flatness, as well as excellent solvent resistance and etching resistance. According to the resist underlayer film of the present invention, since the resist underlayer film is formed from the resist underlayer film forming composition, it is excellent in heat resistance and flatness, as well as solvent resistance and etching resistance. According to the method for forming a resist underlayer film of the present invention, a resist underlayer film having excellent heat resistance and flatness as well as solvent resistance and etching resistance can be obtained. According to the method for producing a patterned substrate of the present invention, the resist underlayer film is formed by using the method for forming the resist underlayer film, so that a substrate having an excellent pattern shape can be obtained. Therefore, these can be suitably used for manufacturing semiconductor devices and the like, which are expected to be further miniaturized in the future.

1 Silicon substrate 2 Membrane 3 Elution curve 4 Baseline

Claims (7)

Compounds represented by the following formula (1) and
A composition for forming a resist underlayer film containing a solvent.
A composition for forming a resist underlayer film in which the ratio of the peak area (A1) containing the above compound to the total peak area (Aa) measured by gel permeation chromatography is 0.25 or more.

(In the formula (1), ^{R 1} and ^{R 10} are each independently a monovalent organic group Der hydrogen atom or C1-30 is, at least one of ^{R 1} and ^{R 10,} Ru der monovalent organic group having 1 to 30 carbon atoms ^{.R 2, R 3,} R ⁴ and ^{R 5} are each independently hydroxy group, a monovalent organic group halogen atoms or 1 to 20 carbon atoms the .n1 and n4 is, the .n2 and n3 is an integer from 0 to 5, an integer of 0 to 4. However, in the case of n1 + n2 + n3 + n4 ≧ 1 and is .n1 is 2 or more, plural ^{R 2} is If may be the same or different .n2 is 2 or more, plural R ^3, if may be the same or different .n3 is 2 or more, plural R ⁴ may be the same or different. If n4 is 2 or more, plural R ⁵ may be the same or different.) The composition for forming a resist underlayer film according to claim 1, wherein the content ratio of the compound to the peak component containing the compound is 90% by mass or more. Claim 1 or claim ^{, wherein at least one of R 2} , R ³ , R ⁴ and R ⁵ of the above formula (1) is a monovalent organic group having an −O— bond and having 1 to 20 carbon atoms. 2. The composition for forming a resist underlayer film according to 2. Any one of claims 1 to 3 in which ^{at least one of R 1} , R ¹⁰ , R ² , R ³ , R ⁴ and R ⁵ of the above formula (1) is a group containing a crosslinkable group. The composition for forming a resist underlayer film according to the item. A resist underlayer film formed from the resist underlayer film forming composition according to any one of claims 1 to 4. A step of applying the resist underlayer film forming composition according to any one of claims 1 to 4 to at least one surface side of the substrate.
A method for forming a resist underlayer film, which comprises a step of heating a coating film formed by the above coating process. A step of forming a resist pattern on the surface side of the resist underlayer film formed by the method for forming the resist underlayer film according to claim 6 opposite to the substrate.
A method for manufacturing a patterned substrate, which comprises a step of performing etching using the resist pattern as a mask.

Images