JPH10239837A - Reflection preventive film material composition and method for forming resist pattern by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance reflection prevention effect, dry etching rate, resolution power, and independence from film thickness by incorporating a polymer light absorber having specified groups on the side chains. SOLUTION: The reflection preventive film material composition contains the polymer light absorber having on the side chains at least one of groups represented by formulae I-IV in which W is a divalent bonding group; each of X1 -X3 is, independently, an H or halogen atom or a cyano or -(X4 )p group; R is a 1-20C alkyl or 6-20C aryl or 7-20C aralkyl group each optionally substituted; X4 is a simple bond or a -CO2 -, -CONH-, -O-, -CO-, 2-4C alkylene, or -SO2 - group; (p) is an integer of 1-10; each of Z1 -Z2 is, independently, an electron donative group; and (m) is 0, 1, or 2, and (n) is 0, 1, 2, or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection coating material composition which is effective in reducing the adverse effects of reflection from an underlying substrate in a lithography process using various radiations.
And a method for forming a resist pattern using the antireflection coating material composition.

[0002]

2. Description of the Related Art A photoresist is a semiconductor wafer,
It is applied to a substrate of glass, ceramic or metal by a spin coating method or a roller coating method to a thickness of 0.5 to 2 μm. After that, it is heated and dried, and the circuit pattern and the like are baked with radiation such as ultraviolet rays through an exposure mask,
An image is formed by performing baking after exposure if necessary and then developing. Further, by etching using this image as a mask, a pattern-like processing can be performed on the substrate. Typical application fields are semiconductor manufacturing processes such as IC,
Manufacturing of circuit boards such as liquid crystal and thermal head, and other photofabrication processes.

In microfabrication of a semiconductor using a photoresist, prevention of light reflection from a substrate surface has become an important issue with miniaturization of dimensions. Conventionally, a photoresist containing a light absorbing agent has been used for this purpose, but there is a problem that the resolution is impaired. Therefore, an anti-reflective coating (Bottom Anti-Reflective Coatin) is placed between the photoresist and the substrate.
g, BARC) has been widely studied. As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and α-silicon, and an organic film type including a light absorbing agent and a polymer material are known. The former is a vacuum evaporation system for film formation, CV
While the latter requires equipment such as a D apparatus and a sputtering apparatus, the latter is advantageous in that it does not require special equipment, and many studies have been made. For example, Japanese Patent Publication 7-6
9611. A condensate of the diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin,
A light absorbing agent or a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680;
JP-A-6-118631, containing a resin binder and a methylolmelamine-based thermal crosslinking agent;
Acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule as described in 18656, a film comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115, and a method described in JP-A-8-179509. Examples thereof include those obtained by adding a low-molecular-weight light absorbing agent to a polyvinyl alcohol resin.

[0004] Physical properties desired as a material for an organic antireflection film include having a large absorbance against radiation,
Insoluble in the photoresist solvent (intermixing with the photoresist layer does not occur), there is no low molecular diffusion material from the antireflective coating material into the overcoated photoresist layer at the time of coating or heating and drying, It may have a higher dry etching rate than photoresist, for example, Proc. SPIE, Vol. 2195, 225-2
29 (1994).

[0005] However, the compounds described in the above patents do not satisfy all of these requirements, and improvements thereof have been desired. For example, in the conventional antireflection film, the light absorption capacity of the binder is not sufficient, and it is necessary to separately increase the amount of the light absorbing agent, or the one containing a large amount of the aromatic light absorbing agent to increase the absorbance has a low dry etching rate. Has problems. Further, those containing a functional group such as a carboxylic acid group which enhances alkali permeability in the cross-linking system have a problem that when development is performed with an alkaline aqueous solution, the antireflection film swells and the resist pattern shape is deteriorated. .

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photoresist exposure light (in particular, a light having a wavelength of 248 nm).
Has a high anti-reflection effect on the surface, and practically no intermixing with the photoresist layer occurs, there is no diffused substance in the photoresist layer during heating and drying, and a high dry etching rate compared to the photoresist. Another object of the present invention is to provide a photoresist antireflection coating material composition and a photoresist pattern forming method capable of obtaining a resist pattern excellent in resolution and film thickness dependency.

[0007]

That is, the object of the present invention is achieved by the following constitution. (1) An antireflective coating material composition comprising a polymer light absorbing agent having at least one of the groups represented by the following general formulas (I) to (VII) in a side chain.

[0008]

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[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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[0015] (In the formula, W is .X ₁ ~, which represents a divalent linking group
X ₃ may be the same or different and represents a hydrogen atom, a halogen atom, a cyano group, or — (X ₄ ) _p —R. Where R
May have a substituent, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to
X ₄ represents a single bond, —CO ₂
- group, -CONH- group, -O- group, -CO- group, an alkylene group or -SO ₂ of 2 to 4 carbon atoms - group, p is an integer of 1 to 10. Z ₁ and Z ₂ may be the same or different and represent an electron donating group. m is 0 to 2 and n is 0
Represents an integer of 1 to 3. When m is 2, n and m are 2 or 3
In the above case, Z ₁ and Z ₂ may be the same or different. A ₁ represents a divalent aromatic or heteroaromatic group having 5 to 14 carbon atoms which may have a substituent.
A ₂ represents an aromatic ring group or a heteroaromatic group having 5 to 14 carbon atoms which may have a substituent. )

(2) A polymer light-absorbing agent having at least one of the structures represented by the following general formulas (VIII) to (XV) as at least a part of a repeating unit of a main chain or a side chain. Anti-reflective coating material composition.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0023]

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[0024]

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(Where X ₁ -X ₃ , Z ₁ , Z ₂ , A ₁ ,
A ₂ , n and m have the same meanings as those described in the above (1). (3) An antireflection coating material composition comprising a polymer light absorbing agent having at least one of the repeating structural units represented by the following general formulas (XVI) to (XVIII).

[0026]

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[0027]

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[0028]

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(In the formula, R ¹ represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or a cyano group. Y represents a divalent linking group. X ₁ , X ₂ , Z ₁ , Z ₂ , m , N, and A ₁ each have the same meaning as in the above (1).)

(4) Y is a single bond or partially-
An alkylene group, an arylene group, an aralkylene group, which may have at least one of a CO ₂ — group, a —CONH— group, a —O— group, a —CO— group, and a —SO ₂ — group;
CO ₂ -E-, -CONH-E-, -OE-, -CO
—E— or —SO ₂ —E— (where E is a single bond or an optionally substituted aromatic ring group having 6 to 14 carbon atoms) The antireflection coating material composition according to the above (3), which is characterized in that:

(5) Z₁, Z_TwoAre the same but different
-OH, -OR^Four, -NR ^FiveR⁶Or -S
R^Four(Where R^FourRepresents a hydrocarbon group having 1 to 20 carbon atoms.
Represents, R^Five, R⁶Is a hydrogen atom or a carbon number of 1 to 20, respectively.
Hydrocarbon groups).
Any of (1) to (4) above,
Anti-reflective coating material composition.

(6) A ₁ or A ₂ is a divalent or monovalent group of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring or a thiophene ring, each of which may have a substituent. Features (1) to above
The anti-reflective coating material composition according to any one of (5).

(7) The polymer light-absorbing agent has the following general formula:
The antireflective coating material composition according to any one of the above (1) to (6), which contains the repeating structural unit represented by (XIX) in an amount of 2% by weight to 50% by weight.

[0034]

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(Wherein, R ² represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or a cyano group. B ₁ has a terminal group of —CH ₂ OH group, —CH ₂ OR ⁷ group, or —CH 2 _Two
Represents an organic functional group having an OCOCH ₃ group. R ⁷ represents a hydrocarbon group having 1 to 20 carbon atoms. )

(8) The polymer light-absorbing agent according to (7)
Wherein B ₁ in the general formula (XIX) described above is -CONHCH _{2
OH, -CONHCH 2 OCH 3, -CH} 2 OCOCH
_{3, -C 6 H 4 (OH} ) CH 2 OH, -C 6 H 4 (O
H) CH ₂ OCH ₃ or -CONHC (CH _{3) 2} C
(1) to (6), wherein the polymer light-absorbing agent contains 2 to 50% by weight of a repeating structural unit which is a group obtained by a reaction between a group represented by H ₂ COCH ₃ and folimarin. The anti-reflective coating material composition according to any one of the above.

(9) The polymer light absorbing agent has the following general formula:
The antireflection coating material composition according to any one of the above (1) to (6), which contains the repeating structural unit represented by (XX) in an amount of 2% by weight to 30% by weight.

[0038]

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(In the formula, R ² represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or a cyano group. B ₂ represents an organic functional group having a terminal epoxy group.)

(10) An antireflective coating material composition comprising the following (a) and (b): (A) the polymeric light-absorbing agent according to any of (1) to (9); and (b) a melamine compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. , Guanamine compounds, glycoluril compounds or urea compounds

(11) An anti-reflective coating material composition comprising the following (a) and (c): (A) the polymer light-absorbing agent according to any one of the above (1) to (9); and (c) a phenol compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. , A naphthol compound or a hydroxyanthracene compound (12) A method for forming a resist pattern, comprising using the antireflection coating material composition according to any one of (1) to (11).

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formulas (I) to (XVIII), a vinyl bond (-C = C
-) (-In the aromatic or heteroaromatic ring of A ₁ and A ₂ )
(Including C = C-) is preferably located at the β-position of the naphthalene ring from the viewpoint of matching with the wavelength (248 nm) of the KrF excimer laser.

In the general formulas (I) to (XVIII), W, Y
Specifically, the divalent linking group may be a single bond,
CO ₂ -group, -CONH- group, -O- group, -CO- group,
—SO ₂ — group, optionally having 1 to 2 carbon atoms
0 straight-chain alkylene group, arylene group, aralkylene group, branched alkylene group having 1 to 20 carbon atoms which may have a substituent, carbon atom having 1 to 2 carbon atoms which may have a cyclic alkylene structure in the middle. Preferred are 20 alkylene groups or a divalent group obtained by combining two or more of the above groups.

The divalent linking group of W and Y is more preferably a -CO ₂ -E- group, a -CONH-E- group, a -O-
E- group, -CO-E- group, -SO ₂ -E- group (wherein,
E is a single bond or a carbon number of 6 to 6 which may have a substituent.
There are 14 aromatic ring groups. ), An optionally substituted alkylene group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Number of arylene group, aralkylene group having 7 to 20 carbon atoms, or these groups and -CO _2, - group, -CONH-
It is a divalent group obtained by combining at least one of a group, a —O— group, a —CO— group, an alkylene group having 2 to 4 carbon atoms, and a —SO ₂ — group. Examples of the alkylene group having 1 to 20 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, laurylene. Group, stearylene group, cyclohexylene group and the like. Examples of the arylene group having 6 to 20 carbon atoms include a phenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group. Examples of the aralkylene group having 7 to 21 carbon atoms include a benzyl group, a naphthylmethyl group, an anthrylmethyl group, and a phenanthrylmethyl group.

The above-mentioned further substituent is preferably an alkyl group having 1 to 10 carbon atoms, an —OH group, an —OR ⁴ group,
Examples include —SR ⁴ groups, —NR ⁵ R ⁶ groups, and halogen groups. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

X _{1 to} X ₃ may be the same or different;
A hydrogen atom, a halogen atom, a cyano group, or — (X ₄ ) _p −
Represents R. Here, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, which may have a substituent;
₄ is a single bond, -CO ₂ - group, -CONH- group, -O-
Group, -CO- group, alkylene group having 2 to 4 carbon atoms or-
Represents an SO ₂ — group, and p represents an integer of 1 to 10. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-lauryl, n-butyl And a stearyl group. Carbon number 6
Examples of the 20 to 20 aryl groups include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
Examples of the aralkyl group having 7 to 21 carbon atoms include a benzyl group, a naphthylmethyl group, an anthrylmethyl group, and a phenanthrylmethyl group.

X _{1 to} X ₃ are preferably a hydrogen atom, a cyano group, a methyl group, an ethyl group, an acetyl group or a benzoyl group.

Z ₁ and Z ₂ are each a substituent of a naphthalene ring and are electron donating groups. The electron donating group is an atom or an atomic group in which Hammett's substituent constant σp shows a negative value. Specifically, -OH group, -OR ⁴ group, -SR ⁴ group,
—NR ⁵ R ⁶ groups and the like. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ each represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms.

Such R ⁴ , R ⁵ and R ⁶ have 1 to 1 carbon atoms.
Examples of the 20 alkyl groups include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-lauryl, n-butyl Stearyl groups and the like can be preferably mentioned. Also, a 2-hydroxyethyl group, an allyl group,
A 2,3-dichloropropyl group and a 2,3-dibromopropyl group are also preferred. Among them, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t
Non-cyclic hydrocarbon groups having 1 to 6 carbon atoms, such as -butyl group, n-pentyl group, n-hexyl group, 2-hydroxyethyl group, allyl group, 2,3-dichloropropyl group, 2,3
-Dibromopropyl groups are particularly preferred. The number of substitution m on the 6-membered ring side to which the vinyl group (-C = C-) is directly connected is 0.
And the substitution number n on the other 6-membered ring side is an integer of 0 to 3. When n is 2 or 3, a plurality of Z ₁ may be the same or different, and when m is 2 or 3, Z ₂ is the same.

In the present invention, A ₁ and A _{2 each} have 5 to 5 carbon atoms.
There are 14 monovalent or divalent aromatic or heteroaromatic ring groups, which may have a substituent. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. And a 5- to 14-membered heteroaromatic ring having an oxygen, nitrogen and sulfur atom in the ring such as a ring and an indazole ring. The aromatic ring or heteroaromatic ring may have, for example, the following substituents. Specifically, for example, carbon number 1
To 20 organic groups. Examples of the organic group include an alkyl group, an alkenyl group, an acyl group, an alkoxy group, and an alkoxycarbonyl group. In addition to organic groups, fluorine, chlorine, bromine, iodine, nitro, cyano, hydroxy,
Examples include an amino group. Further examples include an alkylthio group, an amino group, an N-organoamino group, an N, N-diorganoamino group, and a morpholino group. A ₁ or A ₂ is preferably a group in which a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring or a thiophene ring is a divalent group or a monovalent group.

X ₁ , X ₂ , Z in the formulas (VIII) to (XV)
₁ , Z ₂ , m, n, A ₁ and A ₂ have the same meanings as the above-mentioned groups. In formulas (XVI) to (XVIII), X ₁ ,
X ₂ , Z ₁ , Z ₂ , m, n and A ₁ all have the same meaning as the above-mentioned groups. In the present invention, a polymer light absorbing agent having a repeating structural unit represented by any of the above formulas (XVI) to (XVIII) is preferable.

The amount of the repeating structural unit having a group represented by any of formulas (I) to (XVIII) contained in the total amount of the polymer light absorbing agent is 10 to 99% by weight, preferably 30 to 99% by weight.
To 97% by weight, more preferably 50 to 95% by weight.

Such a polymeric light-absorbing agent has a high antireflection effect because the light-absorbing portion has a sufficient light-absorbing coefficient, and the content of cyclic carbon such as an aromatic ring contained in the light-absorbing portion (part by weight). Rate) is small, and even if the amount of the light-absorbing portion is increased to further increase the absorbance, the decrease in the dry etching rate is small.

The antireflective coating material composition of the present invention contains a polymer light absorbing agent having a substituent represented by the specific structural formula in the side chain or main chain as described above. Such a polymer light-absorbing agent may further have a thermally crosslinkable group substituted in its repeating unit. When a group having a thermal cross-linking reactivity is substituted, intermixing can be more effectively prevented by thermosetting the coating film. Examples of the repeating unit substituting the group having thermal crosslinking reactivity include the repeating units represented by the above general formulas (XIX) and (XX).

In the above formulas (XIX) and (XX), R ² represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or a cyano group.
B ₁ in the formula (XIX) has a —CH ₂ OH group or —
It represents an organic functional group having a CH ₂ OR ⁷ group and a —CH ₂ OCOCH ₃ group. R ⁷ in the —CH ₂ OR ⁷ group has 1 carbon atom
Represents up to 20 hydrocarbon groups. As B ₁ ,
CONHCH ₂ OH group, -CONHCH ₂ OCH ₃ group,
-CH ₂ OCOCH ₃ group, -C ₆ H ₄ CH ₂ OH group, -
A C ₆ H ₄ CH ₂ OCH ₃ group or —CONHC (CH
₃ ) It preferably represents a group obtained by reacting a ₂ CH ₂ COCH ₃ group with formalin. B ₂ in the formula (XX) represents an organic functional group having an epoxy group at a terminal. An example of an epoxy group that is preferably introduced as a thermally crosslinkable group can be exemplified by the following formula.

[0056]

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The content of the repeating structural unit represented by the general formula (XIX) in the polymer light absorbing agent is 2 to 50% by weight, preferably 5 to 30% by weight based on the total weight of the polymer light absorbing agent.
It is. The content of the repeating structural unit represented by the general formula (XX) in the polymer light-absorbing agent is 2 to 30% by weight, preferably 5 to 20% by weight based on the total weight of the polymer light-absorbing agent.

The above-mentioned polymer light-absorbing agent may be copolymerized with a non-crosslinkable repeating unit together with the above-mentioned thermally crosslinkable repeating unit or without containing such a repeating unit. When non-crosslinkable repeating units are copolymerized together, it becomes possible to finely adjust the dry etching rate, the reflectance, and the like. Examples of the monomer forming the non-crosslinkable repeating unit include the following monomers.

For example, compounds having an addition-polymerizable unsaturated bond such as acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonates, etc. It is.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate) , Chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2
-Dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (for example, phenyl acrylate, hydroxyphenyl) Acrylate, etc.);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl Methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylate (eg, phenyl methacrylate, hydroxyphenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, wherein the alkyl group has 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl Group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl group as the aryl group) , A carboxyphenyl group, etc.), N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms,
For example, methyl group, ethyl group, butyl group, isobutyl group,
Examples include an ethylhexyl group and a cyclohexyl group. ),
N, N-arylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N
-Acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Group), N-arylmethacrylamide (the aryl group is a phenyl group,
Examples include a hydroxyphenyl group and a carboxyphenyl group. ), N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, and a butyl group), N, N-diarylmethacrylamide (an aryl group includes a phenyl group, and the like), and N-. Hydroxyethyl-N-methylmethacrylamide, N-methyl-
N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxy Ethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ether (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chloride) Phenyl ether, vinyl 2,4
-Dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichlor acetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl phenyl acetate, vinyl aceto acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .; styrenes, For example, styrene, alkylstyrene (for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropyls Ren, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene,
Benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, Dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3- Trifluoromethylstyrene, etc.), hydroxystyrene (for example, 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, 4-hydroxy-3-methylstyrene) , 4-hydroxy-3,5-dimethylstyrene, 4-hydroxy-3-methoxystyrene, 4-hydroxy-3- (2-hydroxybenzyl)
Styrene), carboxystyrene;

Crotonic esters, such as alkyl crotonates (eg, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); maleic Dialkyl esters of acids or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.) or monoalkyl esters;

Acrylic acid, methacrylic acid, crotonic acid,
Examples include itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile, and the like. In addition, any addition-polymerizable unsaturated compound copolymerizable with the above-mentioned repeating structural unit used in the present invention may be used. Any of these may be used alone or in combination. The above-mentioned polymer light absorbing agent preferably contains a repeating unit introduced from a monomer containing a hydroxyl group. When the repeating unit contains a hydroxyl group in this way, its thermal crosslinkability increases. Examples of monomers capable of forming a repeating unit having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and propylene glycol. Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, or (meth) acrylamide monomers corresponding to the above, vinyl alcohol, hydroxystyrene, hydroxymethylstyrene and the like can be preferably exemplified.

Further, in order to maintain good solvent solubility of the polymer without lowering the dry etching rate, the number of carbon atoms is one.
Alkyl (meth) acrylate monomers having from 10 to 10 alkyl chains are also preferred. N-vinyl carbazole can also be used as a non-crosslinkable monomer.

The content of the non-crosslinkable repeating unit as described above is preferably from 20 to 50 mol%, more preferably from 30 to 40 mol%, in all the repeating units.

Hereinafter, specific examples of the polymer light absorbing agent of the present invention will be shown, but the content of the present invention is not limited thereto.

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[0073]

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The above-mentioned polymer light absorbing agent according to the present invention can be synthesized by a method such as radical polymerization, anionic polymerization, or cationic polymerization. Various forms such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization are possible. As a method for synthesizing a repeating unit having a structure represented by any of the above general formulas (I) to (XVIII), a method in which an amino group is introduced into each light absorbing agent and reacted with (meth) acrylic acid chloride in the presence of a basic catalyst, or the like. Is mentioned. In the present invention,
The polymer light-absorbing agent having the structure represented by any of the general formulas (VIII) to (XV) in the main chain or the side chain is obtained by using a diol or a diamine having a structure represented by the general formula (VIII) to (XV) as a starting monomer And a polymer such as polyester, polyurethane, polyamide, or polyureide obtained by reacting these with a dicarboxylic acid dichloride compound or a diisocyanate compound.

The molecular weight of such a homopolymer or copolymer depends on the coating solvent used, the required solution viscosity,
Depending on the required film shape, etc., the weight average is 10
00 to 1,000,000, preferably 2000 to 3000
00, more preferably 3,000 to 200,000. The content of such a polymer light-absorbing agent in the antireflection coating material composition is 50 to 95% by weight, preferably 70 to 90% by weight, based on the whole solid content.

The anti-reflective coating material of the present invention is applied, for example, on a silicon substrate or the like, and a photoresist layer is applied thereon. In order to prevent interfacial mixing (intermixing) with the photoresist to be overcoated, it is desirable that the applied layer can be cured once when applied on a silicon substrate or the like. For this purpose, it is preferable to mix a thermal crosslinking agent. The following (b) or (c) can be given as examples of the thermal crosslinking agent used together with the above-mentioned polymer light absorbing agent. (B) a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group; and (c) a methylol group, an alkoxymethyl group, Phenol compound, naphthol compound or hydroxyanthracene compound substituted with at least one substituent selected from siloxymethyl group

The number of substituents of the methylol group, alkoxymethyl group and acyloxymethyl group contained in the component (b) is 2 to 6 in the case of a melamine compound, and 2 in the case of a glycoluril compound, a guanamine compound or a urea compound. ~ 4
And preferably 5 to 6 in the case of a melamine compound, and 3 to 4 in the case of a glycoluril compound, a guanamine compound or a urea compound.

All of these methylol group-containing compounds are obtained by reacting melamine, glycoluril, guanamine or urea with formalin in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, ammonia and tetraalkylammonium hydroxide. can get.

The alkoxymethyl group-containing compound can be obtained by heating the above-mentioned methylol group-containing compound in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid and methanesulfonic acid. The acyloxymethyl group-containing compound is obtained by mixing and stirring the methylol group-containing compound with the acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compounds having the above substituents will be described. Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, and 1 to 5 of the methylol group of hexamethylol melamine.
Examples thereof include a compound or a mixture thereof in which methoxymethylation is performed, a compound in which 1 to 5 methylol groups of hexamethoxyethylmelamine, hexaacyloxymethylmelamine, and hexamethylolmelamine are acyloxymethylated or a mixture thereof. As the guanamine compound, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 3 methylol groups of tetramethylolguanamine are methoxymethylated or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine, tetramethylolguanamine, A compound in which 1 to 3 methylol groups are acyloxymethylated, a mixture thereof, and the like.

Examples of the glycoluril compound include tetramethylolglycoluril, tetramethoxymethylglycoluril, a compound in which one to three methylol groups of tetramethylolglycoluril are methoxymethylated or a mixture thereof, and a methylolol group of tetramethylolglycoluril. Or a mixture thereof in which 1 to 3 are acyloxymethylated, or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which one to three methylol groups of tetramethylol urea are methoxymethylated, a mixture thereof, and tetramethoxyethyl urea. These may be used alone or in combination.

The content of (b) in the antireflective coating material composition of the present invention is 2 to 50% by weight, preferably 5 to 30% by weight, based on the solid content.

Next, in the antireflection coating material composition of the present invention, a phenol compound substituted by at least one group selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group, which is contained as the component (c) , A naphthol compound or a hydroxyanthracene compound,
As in the case of the component (b), thermal crosslinking prevents intermixing with the overcoated photoresist and further increases the absorbance of the antireflective coating material composition.

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the component (c) is required to be at least two per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenolic -OH groups A compound in which the positions 2 and 4 are all substituted is preferred. Further, the naphthol compound and the hydroxyanthracene compound serving as the skeleton are represented by O
Those in which the 2-position of the H group is unsubstituted are preferred. The 3- or 5-position of the phenol compound serving as a skeleton may be unsubstituted or may have a substituent. The naphthol compound serving as the skeleton may be unsubstituted or may have a substituent other than the 2-position of the OH group.

These methylol group-containing compounds use, as raw materials, a phenolic -OH group-containing compound in which the 2- or 4-position of the phenolic -OH group is a hydrogen atom, and use this compound as sodium hydroxide, potassium hydroxide, ammonia, It is obtained by reacting with formalin in the presence of a basic catalyst such as tetraalkylammonium hydroxide. Further, the alkoxymethyl group-containing compound can be obtained by heating the above-mentioned methylol group-containing compound in alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, and methanesulfonic acid. The acyloxymethyl group-containing compound is obtained by reacting the methylol group-containing compound with an acyl chloride in the presence of a basic catalyst.

Examples of the skeleton compound include a phenol compound in which the 2- or 4-position of the phenolic -OH group is unsubstituted, naphthol, a hydroxyanthracene compound such as phenol, o-, m-, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol,
Bisphenols such as 3,5-xylenol and bisphenol-A, 4,4′-bishydroxybiphenyl,
TrisP-PA (a product of Honshu Chemical Industry Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene and the like are used.

Specific examples of the component (c) include trimethylolphenol, tri (methoxymethyl) phenol, a compound in which one or two methylol groups of trimethylolphenol are methoxymethylated, and trimethylol-
A compound in which one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol and trimethylol-3-cresol are methoxymethylated, dimethylol cresol such as 2,6-dimethylol-4-cresol, Tetramethylol bisphenol-A, tetramethoxymethyl bisphenol-A, a compound in which 1 to 3 methylol groups of tetramethylol bisphenol-A are methoxymethylated, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4 ,
4'-bishydroxybiphenyl, hexamethylol form of TrisP-PA, hexamethoxymethyl form of TrisP-PA Compound in which 1 to 5 methylol groups of hexamethylol form of TrisP-PA are methoxymethylated, bishydroxymethylnaphthalenediol Etc. Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene. As the acyloxymethyl group-containing compound, for example, a compound in which the methylol group of the methylol group-containing compound is partially or entirely acyloxymethylated is exemplified.

Among these compounds, preferred are trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, Tris
Hexamethylol of P-PA (product of Honshu Chemical Industry Co., Ltd.) or those methylol groups are alkoxymethyl groups,
And a phenol compound substituted with both a methylol group and an alkoxymethyl group. These may be used alone or in combination. The content of the component (c) in the composition of the present invention is 2 to 50% by weight, preferably 5 to 30% by weight, based on the solid content.

The antireflective coating composition of the present invention may further contain, if necessary, a light absorbing agent, an adhesion aid and a surfactant. As a light absorbing agent to be added to the above composition, for example, “Technology and market of industrial dyes” (CMC Publishing)
And commercially available light-absorbing agents described in Dye Handbook (edited by Organic Synthetic Chemistry Association). For example, C.I. I. Disp
erse Yellow 1,3,4,5,7,8,1
3,23,31,49,50,51,54,60,6
4,66,68,79,82,88,90,93,10
2,114 and 124, C.I. I. Disperse O
range 1,5,13,25,29,30,31,
44, 57, 72 and 73, C.I. I. Disperse
Red 1,5,7,13,17,19,43,5
0, 54, 58, 65, 72, 73, 88, 117, 1
37, 143, 199 and 210, C.I. I. Dispe
rse Violet 43, C.I. I. Dispers
e Blue 96, C.I. I. Fluorescent
Brightening Agent 112,13
5 and 163, C.I. I. Solvent Orange
2 and 45, C.I. I. Solvent Red 1,
3, 8, 23, 24, 25, 27 and 49, C.I. I. P
Pigment Green 10, C.I. I. Pigme
nt Brown 2 or the like can be suitably used.
The light absorbing agent is usually based on 100 parts by weight of the antireflection coating composition.
50 parts by weight or less, preferably 30 parts by weight or less.

The adhesion aid is mainly added for the purpose of improving the adhesion between the substrate or the resist and the antireflection film composition, and particularly preventing the resist from peeling off in the etching step. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenylsilane. Alkoxysilanes such as enyltriethoxysilane, silazane such as hexamethyldisilazane, N, N'-bis (trimethylsilin) urea, dimethyltrimethylsilylamine and trimethylsilylimidazole, vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ
Silanes such as glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, urazole thiouracil, mercaptoimidazole, mercapto Examples include a heterocyclic compound such as pyrimidine, a urea such as 1,1-dimethylurea and 1,3-dimethylurea, and a thiourea compound. These adhesion aids are used in the anti-reflective coating composition 100
It is usually blended in a proportion of less than 10 parts by weight, preferably less than 5 parts by weight based on parts by weight.

The antireflective coating composition of the present invention may contain a surfactant for further improving the coating properties of a striation and the like. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and polyoxyethylene nonyl. Polyoxyethylene alkyl allyl ethers such as phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sol Monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, Efutotsupu EF301, EF3
03, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florado FC430, FC431 (Sumitomo 3M Limited)
Made), Asahi Guard AG710, Surflon S-38
2, SC101, SC102, SC103, SC10
Fluorinated surfactants such as 4, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP3
No. 41 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No. 41 75, N
o. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. Among these surfactants, fluorine surfactants and silicon surfactants are particularly preferred. The amount of these surfactants is 10% solids in the composition of the present invention.
It is usually at most 2 parts by weight, preferably at most 1 part by weight, per 0 parts by weight.

These surfactants may be added alone or in some combination. The antireflective coating composition of the present invention comprising a polymer light absorbing agent, a light absorbing agent, an adhesion aid, a surfactant and the like is usually used after being dissolved in an appropriate solvent. As a solvent for dissolving these, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, toluene, Xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxypropion Acid, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Chill,
Methyl 3-ethoxypropionate, methyl pyruvate,
Ethyl pyruvate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and the like can be used. These organic solvents are used alone or in combination of two or more. Further, a mixture of a high boiling point solvent such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether may be used. it can. Among these solvents, propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate and ethyl lactate are preferred from the viewpoint of safety.

The antireflection coating composition of the present invention is usually used as follows. That is, the anti-reflective coating composition is dissolved in the above solvent to a concentration of about 10% by weight, and the substrate (eg, silicon /
An anti-reflection film is formed by applying a suitable coating method such as a spinner or a coater on a silicon dioxide skin cover, a glass substrate, a transparent substrate such as an ITO substrate, or the like. When the composition contains a thermal crosslinking agent, or when the polymer light absorbing agent has a thermal crosslinking substituent, after application, the coating is heated to a predetermined temperature to cure the coating. . The thickness of the antireflection film is preferably from 0.01 to 3.0 μm. The heating temperature after application is 80 to 250 ° C., and the heating time is 1 to 12.
0 minutes. A photoresist is applied on the anti-reflection film thus obtained, and then, through a predetermined mask,
Expose. Here, as the exposure light source, for example, 365 nm
The wavelength light of i is mercury i-line, the wavelength of 248 nm is KrF excimer laser light, and the wavelength of 193 nm is ArF excimer laser light. Heat as needed (PEB: Post Exposure Bak)
e) Then, development is performed using a developer. Then, rinse and dry to obtain a photoresist.

In the present invention, as the resist applied on the antireflection film, both negative and positive resists can be used, but a binder having a group which is decomposed by a photoacid generator and an acid to increase the alkali dissolution rate is used. A chemically amplified resist composed of a low molecular weight compound which is decomposed by an alkali-soluble binder, a photoacid generator and an acid to increase the alkali dissolution rate of the resist,
Alternatively, a chemically amplified resist composed of a binder having a group that increases the alkali dissolution rate by decomposing with a photoacid generator and an acid and a low molecular compound that decomposes with an acid and increases the alkali dissolution rate of the resist is preferable. ARCH-2 manufactured by Fuji Hunt Microelectronics Inc. may be mentioned.

The developer of the positive photoresist composition adapted to the antireflection coating composition of the present invention includes inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia. Alkalis, ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine and the like Alcohol amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline,
Aqueous solutions of alkalis such as cyclic amines such as pyrrole and piperidine can be given. Further, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a nonionic surfactant may be added to an aqueous solution of the above alkalis. Of these developers, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are more preferred.

[0097]

The present invention will now be described by way of examples, which should not be construed as limiting the invention. Synthesis Example 1 The polymer light absorbing agent shown in the specific example (8) was synthesized. Monomer synthesis 204 g of 1-phenylnaphthalene were nitrated with nitric acid in 1 liter of acetic acid. The product was reduced using reduced iron to obtain 1- (4-aminophenyl) naphthalene.
(Yield 39%) After 110 g of the above amine and 55 g of acryloyl chloride were added to 600 ml of acetone, 51 g of triethylamine was added dropwise. After reacting at 40 ° C. for 4 hours, 2 liters of distilled water was added, and the precipitated product was collected by filtration.
(Yield: 75%) Polymer Synthesis After dissolving 10 g of the above monomer and 8 g of N-methylolacrylamide in 40 g of DMF, the reaction solution was heated to 65 ° C., and simultaneously, nitrogen was allowed to flow through the reaction solution for 30 minutes. V-65 (product of Wako Pure Chemical Industries, Ltd.) as a polymerization initiator 50 m
g was added three times every two hours. The reaction product was recovered as a powder by reprecipitation in 1 liter of distilled water. GPC analysis of the obtained polymer showed that the weight average molecular weight was 24,000 in terms of standard polystyrene.

Synthesis Example 2 The polymer light absorbing agent shown in the specific example (9) was synthesized. Monomer Synthesis 202 g of 1-bromo-4-nitrobenzene and 207 g of 2-bromonaphthalene were subjected to Ullman coupling using a copper catalyst. The product was purified by column chromatography to obtain 2- (4-nitrophenyl) naphthalene. The product was reduced using reduced iron to obtain 2- (4-aminophenyl) naphthalene. (Yield 36%) After 109 g of the above amine and 55 g of acryloyl chloride were added to 600 ml of acetone, 51 g of triethylamine was added dropwise. After reacting at 40 ° C. for 4 hours, 2 liters of distilled water was added, and the precipitated product was collected by filtration.
(Yield 68%) Polymer Synthesis 10 g of the above monomer, 8 g of 2-hydroxyethyl methacrylate and 4 g of methyl methacrylate were combined with 40 g of DMF.
After the reaction, the reaction solution was heated to 65 ° C., and nitrogen was passed through the reaction solution for 30 minutes. V-6 as a polymerization initiator
5 (Wako Pure Chemical Industries, Ltd. product) 50 mg every 2 hours 3
Added several times. The reaction product was recovered as a powder by reprecipitation in 1 liter of distilled water. GP of the obtained polymer
C analysis revealed that the weight average molecular weight was 48,000 in terms of standard polystyrene.

Synthesis Example 3 The polymer light absorbing agent shown in the specific example (4) was synthesized. Monomer Synthesis 50 g of (4-nitrobenzyl) triphenylphosphonium bromide and 6-methoxy-2-naphthaldehyde 1
8.6 g was dissolved in ethanol, and 54 g of sodium ethoxide was added thereto and reacted. Water was added to precipitate crystals. (Yield 67%) In the obtained crystals, nitro groups were reduced to amino groups using reduced iron in acetic acid. The obtained aniline compound was converted into a methacrylamide type monomer with methacrylic acid chloride and triethylamine in DMF. Polymer synthesis 10 g of the above monomer, 6 g of 2-hydroxyethyl methacrylate and 4 g of methyl methacrylate were combined with 40 g of DMF.
After the reaction, the reaction solution was heated to 65 ° C., and nitrogen was passed through the reaction solution for 30 minutes. V-6 as a polymerization initiator
5 (Wako Pure Chemical Industries, Ltd. product) 50 mg every 2 hours 3
Added several times. The reaction product was recovered as a powder by reprecipitation in 1 liter of distilled water. GP of the obtained polymer
C analysis revealed a weight average molecular weight of 21,000 in terms of standard polystyrene.

Synthesis Example 4 The polymer light absorbing agent shown in the specific example (12) was synthesized. 1-
9.44 g of hydroxy-2- (4-hydroxyphenyl) -naphthalene, 5.40 g of 1,4-butanediol,
16.8 g of hexamethylene diisocyanate was dissolved in 100 g of dimethylacetamide. After adding 0.02 g of n-butyltin dilaurate as a catalyst, 160
Reaction was performed by heating to ° C. The product was recovered by water reprecipitation. It was 4,900 when the molecular weight was measured by GPC (THF solvent system).

Synthesis of Comparative Example 1 208 g of 9-hydroxymethylanthracene, 101 g of triethylamine and 1 g of hydroquinone were dissolved in 1 liter of DMF. 90 g of acryloyl chloride was added dropwise thereto over 2 hours so that the temperature of the reaction solution did not exceed 30 ° C. 2 L of distilled water was added, and the precipitated crude crystals were collected by filtration. The crude crystals were recrystallized with ethanol-water. (Yield 75%) 7 g of the obtained acrylic monomer and methyl acrylate 1
After dissolving 2 g in 60 g of DMF, the reaction solution was heated to 65 ° C., and nitrogen was passed through the reaction solution for 30 minutes. V-65 (product of Wako Pure Chemical Industries, Ltd.) as a polymerization initiator 50 m
g was added three times every two hours. The reaction product was recovered as a powder by reprecipitation in 1 liter of distilled water. GPC analysis of the obtained polymer showed a weight average molecular weight of 4,000 in terms of standard polystyrene.

Examples 1 to 3 and Comparative Example 1 Synthesis Examples 1 to
After dissolving 18 g of the polymer obtained in Step 3 and 2 g of hexamethoxymethylmelamine in ethoxyethyl propionate to form a 10% solution, the solution was filtered using a Teflon microfilter having a pore diameter of 0.10 μm to prepare an antireflection coating solution. did. This was applied on a silicon wafer using a spinner. Heating was performed at 170 ° C. for 3 minutes on a vacuum contact hot plate to form an antireflection film. (However, only the compound of Synthesis Example 1 (Specific Example 8) did not contain the heat-crosslinking agent hexamethoxymethylmelamine.) Similarly, an antireflection coating solution was prepared from the polymer obtained in the synthesis of Comparative Example 1. .

[Examples 4 to 6] Instead of hexamethoxymethylmelamine of Examples 1 to 3, 2.0 g of a hexamethylol derivative of TrisP-PA (a product of Honshu Chemical Industry Co., Ltd.)
The antireflection coating solutions of Examples 4 to 6 were obtained in the same manner as in Examples 1 to 3, respectively. The antireflection coating solutions of Examples 4 to 6 were filtered using a Teflon microfilter having a pore diameter of 0.10 μm, and then applied to a silicon wafer using a spinner. 1 on vacuum contact hot plate
Heating was performed at 70 ° C. for 3 minutes to form an antireflection film. Example 7 In the same manner as in Examples 1 to 3, an antireflection film containing the polymer of the specific example (12) obtained in Synthesis Example 4 was formed. However, the solvent used was cyclohexanone instead of ethoxyethyl propionate.

The thickness of the antireflection film was 0.17 μm.
It was prepared. Then, these antireflection films were immersed in a coating solvent used for the resist, for example, γ-butyrolactone or ethoxyethyl propionate, and were confirmed to be insoluble in the solvent.

On the obtained antireflection film, ARCH-2 was used as a positive photoresist for a KrF excimer laser.
After coating (Fuji Hunt Electronics Technology Co., Ltd. product) (film thickness 0.85 μm), using a reduction projection exposure apparatus (Nikon Corporation NSR-1505EX),
After exposure to light having a wavelength of 248 nm, post-exposure heat treatment was performed at 110 ° C. for 60 seconds, followed by development with a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute and drying for 30 seconds. The resist pattern on the silicon wafer thus obtained was observed with a scanning electron microscope, and the critical resolution and the film thickness dependency were examined. 2
The absorbance at 48 nm was measured by applying an antireflection film composition on a quartz plate and drying by heating to form a film, and using a spectrophotometer UV-240 manufactured by Shimadzu Corporation.

The critical resolution means a critical resolution at an exposure amount for reproducing a 0.5 μm mask pattern at a resist film thickness of 0.85 μm. The film thickness dependency is used to evaluate the effect of the difference in film thickness on the sensitivity, and is evaluated based on the ratio of the sensitivity at a resist film thickness of 0.85 μm to the sensitivity at a film thickness of 0.87 μm. The closer this value is to 1.0, that is, the lower the dependency, the better. The dry etch rate was determined by applying an anti-reflective coating composition on a silicon wafer, heating and drying to form a film, and then applying it to CS manufactured by Nippon Vacuum Engineering Co., Ltd.
It was measured under CF ₄ / O ₂ conditions by E-1110. Table 1 shows the results of these evaluations.

[0107]

[Table 1]

As a result, the antireflection coating composition of the present invention has high film absorbance, improves the critical resolution of the photoresist, and reduces the dependency of the sensitivity caused by the standing wave due to the reduction of the reflected light from the substrate on the film thickness. I understand. On the other hand, in Comparative Example 1, the above effect was not obtained.

[0109]

According to the antireflection coating material composition and the photoresist pattern forming method of the present invention, the effect of preventing reflection of light is high, intermixing with the photoresist layer does not occur, and the photoresist is substantially dried during heating and drying. There is no diffused substance in the resist layer, the dry etching rate is higher than that of the photoresist, the resolving power and the film thickness dependency are excellent, and a fine image can be accurately drawn on a predetermined substrate.

Claims (12)

[Claims] 1. An anti-reflective coating material composition comprising a polymer light absorbing agent having at least one of the groups represented by the following general formulas (I) to (VII) in a side chain. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image (In the formula, W represents a divalent linking group. X _{1 to} X ₃ may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, or — (X ₄ ) _p —R. , R may be substituted, represents alkyl group having 1 to 20 carbon atoms, the number 6 to 20 aryl group or having 7 to 20 carbon atoms or aralkyl group having a carbon X ₄ is a single bond , -CO ₂ -group, -C
ONH- group, -O- group, -CO- group, an alkylene group or -SO ₂ of 2 to 4 carbon atoms - group, p is an integer of 1 to 10. Z ₁ and Z ₂ may be the same or different and represent an electron donating group. m represents an integer of 0 to 2 and n represents an integer of 0 to 3. When m is 2, n, when m is 2 or 3,
Z ₁ and Z ₂ may be the same or different. A ₁ has a divalent carbon number of 5 to 5 which may have a substituent.
Represents 14 aromatic ring groups or heteroaromatic ring groups. A ₂ represents an aromatic ring group or a heteroaromatic group having 5 to 14 carbon atoms which may have a substituent. ) 2. A polymer light-absorbing agent having at least one of the structures represented by the following general formulas (VIII) to (XV) as at least a part of a main chain or a side chain repeating unit. Anti-reflective coating material composition. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image (Where X _{1 to} X ₃ , Z ₁ , Z ₂ , A ₁ , A ₂ , n, m
Are the same as those described in claim 1. ) 3. An antireflection coating material composition comprising a polymer light absorbing agent having at least one of the repeating structural units represented by the following general formulas (XVI) to (XVIII). Embedded image Embedded image Embedded image (Wherein, R ¹ represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or a cyano group; Y represents a divalent linking group; X
₁ , X ₂ , Z ₁ , Z ₂ , m, n and A ₁ have the same meanings as in claim 1 respectively. ) 4. Y is a single bond or partially —CO ₂
-Group, -CONH- group, -O- group, -CO- group or-
An alkylene group, an arylene group, an aralkylene group, —CO ₂ , which may have one or more SO ₂ — groups;
-E-, -CONH-E-, -OE-, -CO-E-
Or -SO ₂ -E- (where E is a single bond or an optionally substituted aromatic ring group having 6 to 14 carbon atoms). The anti-reflective coating material composition according to claim 3, wherein 5. Z₁, Z_TwoMay be the same or different
-OH, -OR ^Four, -NR^FiveR⁶Or -SR
^Four(Where R^FourRepresents a hydrocarbon group having 1 to 20 carbon atoms.
Then R^Five, R⁶Are each a hydrogen atom or 1 to 20 carbon atoms
Which is a hydrocarbon group)
The antireflection according to any one of claims 1 to 4, wherein
Film-blocking material composition. 6. A ₁ or A ₂ is a divalent or monovalent group of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring or a thiophene ring, each of which may have a substituent. The anti-reflective coating material composition according to claim 1. 7. The polymer light-absorbing agent has the following general formula (XIX):
The antireflective coating material composition according to any one of claims 1 to 6, wherein the composition contains 2 to 50% by weight of a repeating structural unit represented by the formula: Embedded image (Wherein, R ² represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or a cyano group. B ₁ has —CH ₂ O
H group, —CH ₂ OR ⁷ group, or —CH ₂ OCOCH ₃
Represents an organic functional group having a group. R ⁷ represents a hydrocarbon group having 1 to 20 carbon atoms. ) 8. The polymer light-absorbing agent according to claim 7, wherein B ₁ in the general formula (XIX) is -CONHCH ₂ OH,-
CONHCH ₂ OCH ₃ , —CH ₂ OCOCH ₃ , —C
_{6 H 4 (OH) CH 2} OH, -C 6 H 4 (OH) CH 2
OCH ₃ or _{-CONHC (CH 3) 2 CH 2} COC
To claim 1, characterized in that a polymeric absorber of the repeating structural unit containing 50 wt% 2 wt% reactive a group obtained by the group and formalin represented by H ₃ The anti-reflective coating material composition according to the above. 9. The method according to claim 1, wherein the polymer light-absorbing agent contains a repeating structural unit represented by the following general formula (XX) in an amount of 2% by weight to 30% by weight. Anti-reflective coating material composition. Embedded image (In the formula, R ² represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or a cyano group. B ₂ represents an organic functional group having a terminal epoxy group.) 10. An antireflective coating material composition comprising the following (a) and (b): (A) the polymer light-absorbing agent according to any one of claims 1 to 9; (b) a melamine compound or a guanamine compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. , Glycoluril compounds or urea compounds 11. An antireflective coating material composition comprising the following (a) and (c): (A) the polymer light-absorbing agent according to any one of claims 1 to 9 (c) a phenol compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, naphthol Compound or hydroxyanthracene compound 12. A method of forming a resist pattern, comprising using the antireflection coating material composition according to claim 1. Description: