JP2007241259A - Resist underlayer coating forming composition for mask blank, mask blank, and mask - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist underlayer coating forming composition used in steps of manufacturing a mask blank and a mask, and to provide a mask blank and a mask manufactured from the composition. <P>SOLUTION: The resist underlayer coating forming composition comprises a polymer compound having a halogen atom-containing repeating structural unit and a solvent. In a mask blank including a thin film for forming a transfer pattern and a chemically-amplified resist coating on a substrate in that order, the above composition is used for forming a resist underlayer coating between the thin film for forming a transfer pattern and the resist coating. The polymer compound contains a halogen atom in an amount of at least 10 mass%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resist underlayer film forming composition used for a mask blank having a resist underlayer film under a chemically amplified resist film. Specifically, the present invention relates to a resist underlayer film forming composition containing a polymer compound having a repeating unit structure containing a halogen atom and a solvent. Furthermore, the present invention relates to a mask blank on which a resist underlayer film made of the composition for forming a resist underlayer film is formed, and a mask produced using the mask blank.

  A photomask (reticle) used in a microfabrication technique for semiconductor devices is manufactured by patterning a light-shielding film formed on a transparent substrate. The patterning of the light shielding film is performed by, for example, etching using a resist pattern as a mask. The resist pattern is formed by, for example, an electron beam lithography method.

  In recent years, in the field of mask manufacturing, it has been studied to increase the acceleration voltage of an electron beam used in the electron beam lithography method to 50 eV or more. This is because it is necessary to reduce the forward scattering of the electron beam passing through the electron beam resist and to improve the focusing property of the electron beam so that a finer resist pattern can be resolved. . When the acceleration voltage of the electron beam is low, forward scattering occurs on the resist surface or in the resist, and when there is forward scattering, the resolution of the resist deteriorates. However, when the acceleration voltage of the electron beam is set to 50 eV or more, forward scattering decreases in inverse proportion to the acceleration voltage, and the energy imparted to the resist by forward scattering decreases. For example, the acceleration voltage of 10 to 20 eV is used. The electron beam resist that has been used lacks the sensitivity of the resist, resulting in a decrease in throughput.

  Here, when a chemically amplified resist film is used in the mask manufacturing field, for example, if the film density near the surface of the base film is relatively sparse or rough, the problem of deactivation of the chemically amplified resist film may occur. It is known that can occur. Specifically, the acid catalyst reaction during patterning may be inhibited at the interface between the resist film and the chromium oxide anti-reflection film or the like serving as a base film, and the resolution may deteriorate at the bottom of the resist pattern. In this case, for example, a shape defect such as tailing occurs in a positive chemically amplified resist film and biting occurs in a negative type resist film.

  This is because, for example, the acid generated in the resist film by exposure is suppressed (quenched) by the base component on the surface of the chromium oxide, or the acid diffuses to the chromium oxide side. This is thought to be because the sensitivity of the chemically amplified resist film at the interface apparently decreases (deactivation of the resist film).

  As a method of solving the above-mentioned problem of shape defects, a configuration in which an inorganic film of a silicide-based material or an organic anti-reflection film is introduced as a lower layer film (deactivation suppression film) under a chemically amplified resist film is reported. (For example, refer to Patent Document 1).

On the other hand, Patent Document 2 discloses an antireflection film-forming composition containing a polymer material containing a halogen atom for forming an antireflection film having strong absorption with respect to light having a wavelength of 157 nm.
JP 2003-107675 A International Publication No. 03/071357 Pamphlet

  When the lower layer film is formed under the resist film as in the invention described in Patent Document 1, the patterning resolution of the light-shielding film may be deteriorated due to the influence of the resist lower layer film. Observed. For example, when the resist underlayer film and the light-shielding film are etched using the resist pattern of the chemically amplified resist film as a mask, the resist film is also etched during the etching of the resist underlayer film, resulting in resist pattern resolution. There was a decline.

  In this case, even if the resolution of the resist pattern immediately after the formation is high, the resolution of the resist pattern is reduced when the light shielding film is etched. This also reduces the patterning resolution of the light-shielding film etched using this resist pattern as a mask.

  That is, even if the problem of the above-mentioned shape defects such as tailing and erosion caused by using a chemically amplified resist film as a mask blank is solved by forming a resist underlayer film, by forming a resist underlayer film, It has been found that this may cause a new problem that the resolution of patterning of the light-shielding film cannot be sufficiently improved.

  In addition, when the problem caused by using the chemically amplified resist film as a mask blank itself was examined, the adhesion between the resist film and the underlayer could not be sufficiently obtained depending on the composition of the underlayer of the resist film. It was observed that there was a case. For example, when the base film is a silicide film, the adhesion between the resist film and the base film is insufficient, and the resist pattern may disappear during development. Further, the coatability is not sufficient, and it may be difficult to form a uniform resist film.

  Therefore, the present invention can solve the above-mentioned problem that occurs when a chemically amplified resist film is used as a mask blank, i.e., patterning of a thin film that forms a transfer pattern without causing shape defects such as tailing and biting. It is an object to provide a resist underlayer film forming composition used for a resist underlayer film formed under a resist film, which can sufficiently improve resolution and has excellent adhesion to a resist film and other underlayer films. Furthermore, it is an object of the present invention to provide a mask blank and a mask that can sufficiently improve patterning resolution of a thin film that forms a transfer pattern without causing shape defects such as skirting and biting.

As a first aspect, the present invention provides a resist underlayer film forming composition for use in a mask blank formed on a substrate in the order of a thin film for forming a transfer pattern, a resist underlayer film, and a chemically amplified resist film. A resist underlayer film forming composition comprising a polymer compound having a repeating unit structure containing atoms and a solvent,
As a second aspect, the resist underlayer film forming composition according to the first aspect, in which the polymer compound contains at least 10% by mass of a halogen atom,
As a third aspect, the polymer compound has the formula (1):
(Wherein, L represents a bonding group constituting the main chain of the polymer compound, M represents a direct bond, or -C (= O) -, - CH 2 - comprises at least one selected or from -O- Q is an organic group, and at least one of L, M, and Q contains a halogen atom, V is the number of unit structures contained in the polymer compound, and is a number from 1 to 3000. The resist underlayer film forming composition according to the first aspect or the second aspect, which is represented by:
As a fourth aspect, the resist underlayer film forming composition according to the third aspect, wherein L is a main chain of an acrylic or novolac polymer compound,
As a fifth aspect, the resist underlayer film forming composition according to any one of the first aspect to the fourth aspect, in which the halogen atom is a chlorine atom, a bromine atom, or an iodine atom,
As a sixth aspect, the resist underlayer film forming composition according to any one of the first to fifth aspects, which further contains a crosslinking agent and a crosslinking catalyst in the polymer compound and the solvent,
As a seventh aspect, the resist underlayer film forming composition according to any one of the first aspect to the sixth aspect, wherein the polymer compound and the solvent further contain an acid generator,
As an eighth aspect, the resist underlayer film forming composition according to any one of the first aspect to the seventh aspect, wherein the polymer compound has a weight average molecular weight of 700 to 1,000,000.
As a ninth aspect, a mask blank in which a thin film for forming a transfer pattern and a resist underlayer film are sequentially formed on a substrate, the resist underlayer film according to any one of the first to eighth aspects. A mask blank, which is a resist underlayer film formed from a resist underlayer film forming composition,
As a tenth aspect, the thin film forming the transfer pattern is made of a material containing chromium, and the mask blank according to the ninth aspect,
As an eleventh aspect, the mask blank is a thin film that forms the transfer pattern by dry etching treatment of chlorine-containing gas containing chlorine with a resist pattern formed by a chemically amplified resist formed on the resist underlayer film as a mask. The mask blank according to the ninth aspect or the tenth aspect, which is a mask blank for dry etching processing corresponding to a mask manufacturing method for patterning,
As a twelfth aspect, the mask blank according to any one of the ninth aspect to the eleventh aspect, wherein a chemically amplified resist film is formed on the resist underlayer film,
A thirteenth aspect is a mask comprising a mask pattern formed by patterning a thin film forming the transfer pattern in the mask blank according to any one of the ninth aspect to the twelfth aspect.

The resist underlayer film obtained by the resist underlayer film forming composition of the present invention can obtain a good resist pattern because it does not inhibit the acid-catalyzed reaction during patterning, and is sufficient compared to the resist coated on the upper layer. Since the resist film is not etched during the etching of the lower layer film, the thin film forming the transfer pattern can be etched while maintaining the resolution of the resist pattern immediately after the formation of the resist film. As a result, the resolution of patterning of the thin film forming the transfer pattern can be improved.
Moreover, the underlayer film formed using the resist underlayer film forming composition of the present invention is excellent in adhesion to the resist film and other underlayer films.
The resist underlayer film in the mask blank of the present invention requires the effect of preventing reflected light as opposed to the antireflection film in the semiconductor manufacturing process for preventing reflected light generated from the substrate. However, by forming it under the mask blank resist, it is possible to form a clear mask pattern during exposure of the resist with an electron beam.

  The present invention is used for manufacturing a mask blank on which a chemically amplified resist film is formed, and is used for forming a thin film that forms a transfer pattern on a substrate and a resist underlayer film between the resist films. A resist underlayer film forming composition comprising a polymer compound having a repeating unit structure containing atoms and a solvent.

  The resist underlayer film forming composition of the present invention basically comprises a polymer compound having a repeating unit structure containing a halogen atom and a solvent, and a polymer having a repeating unit structure containing a halogen atom and a cross-linking substituent. A compound consisting of a compound and a solvent, or a polymer compound having a repeating unit structure containing a halogen atom and a repeating unit structure containing a cross-linking substituent, and a solvent, and optionally includes a crosslinking catalyst and a surfactant. Etc. are contained. Solid content of the resist underlayer film forming composition of this invention is 0.1-50 mass%, Preferably it is 0.5-30 mass%. The solid content is obtained by removing the solvent component from the resist underlayer film forming composition.

  Content in the resist underlayer film forming composition of the said high molecular compound is 20 mass% or more in solid content, for example, 20-100 mass%, or 30-100 mass%, or 50-90 mass%, or 60-80. % By mass.

  Moreover, a high molecular compound contains a halogen atom of at least 10 mass%, Preferably it is 10-80 mass%, More preferably, it is 20-70 mass%.

  The halogen atom is contained in the L portion corresponding to the main chain, the M portion corresponding to the linking group, the Q corresponding to the organic group, or a combination thereof in Formula (1).

  The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a chlorine atom, a bromine atom, an iodine atom, or a combination thereof is particularly preferable.

  The polymer compound may include a cross-linking substituent. Examples of such a cross-linking substituent include a hydroxyl group, an amino group, a carboxyl group, a thiol group, and a methoxy group, and this substituent is introduced into the main chain and / or side chain of the polymer compound.

  The introduced crosslinking-forming substituent can cause a crosslinking reaction with the crosslinking agent component introduced into the resist underlayer film-forming composition of the present invention upon heating and baking. The resist underlayer film formed by such a crosslinking formation reaction has an effect of preventing intermixing with the resist film coated on the upper layer.

  The polymer compound containing a halogen atom can be synthesized by a polymerization reaction of a unit monomer containing a halogen atom, or a copolymerization reaction of a unit monomer containing a halogen atom and a unit monomer not containing a halogen atom.

  In the case where no crosslink forming substituent is present in the unit monomer containing a halogen atom, the crosslink forming substituent can be present in the unit monomer not containing a halogen atom.

  The unit monomer used in the polymerization reaction may be the same type, but two or more types of unit monomers may be used. The polymer compound formed from the unit monomer can be synthesized by methods such as radical polymerization, anionic polymerization, cationic polymerization, and degeneracy. The form can be a method such as solution polymerization, suspension polymerization, emulsion polymerization or bulk polymerization.

  Examples of unit monomers having a halogen atom include acrylic acids, acrylic esters, acrylic amides, methacrylic acids, methacrylic acids, methacrylic esters, methacrylic amides, vinyl ethers, vinyl alcohols, styrenes, and benzene. , Phenols, naphthalenes, naphthanols and the like.

Examples of unit monomers that do not contain halogen atoms include acrylic acids, acrylic esters, acrylic amides, methacrylic acids, methacrylic acids, methacrylic esters, methacrylic amides, vinyl ethers, vinyl alcohols, styrene. Benzenes, phenols, naphthalenes, naphthanols and the like.

Although there will be no restriction | limiting in particular if L is a coupling group which comprises the principal chain of a high molecular compound in the structure of Formula (1), For example, the following (a-1)-(a-11) can be illustrated. .
In the above formula, v is the number of repeating units and is 1 to 3000, n is the number of halogen atoms substituted on the benzene ring or naphthalene ring, the number is 1 or more, and can be substituted. Indicates any integer up to the maximum number.

M in the formula (1) is a direct bond or, for example, —C (═O) —, —C (═O) O—, —CH ₂ —, —CH (I) —, —O—, —C. (═O) O—CH ₂ —, —C (═O) —NH—, —C (═O) —NH—CH ₂ —, —OC (═O) —, or —OC (═O) —CH Linking groups such as _2- , and (b-1) to (b-10):
Can be illustrated.

In addition, the Q part in the formula (1) is a halogen atom or, for example, (c-1) to (c-10):
The organic group which has the halogen atom of can be illustrated.

Specific examples of the repeating unit structure containing a halogen atom contained in the polymer compound are shown below.
In the formulas [3-1] to [3-27], n represents the number of halogen atoms, 1 to 5 for a benzene ring, 1 to 7 for a naphthalene ring, and 1 to 9 for an anthracene ring.

In addition, when the polymer compound containing a halogen atom does not have a crosslink forming group, a monomer of a repeating unit having no halogen atom and having a crosslink forming group can be copolymerized. Their monomer structure is, for example,
Is mentioned.

Specific examples of the polymer compound used in the resist underlayer film forming composition of the present invention are shown below.
In [5-1] to [5-55], v1, v2, and v3 represent the number of repeating units, each being 1 or more, and the total number of repeating units of v1, v1 + v2, v1 + v2 + v3 is 3000 or less. is there.

(1-1) to (1-34), (2-1) to (2-30), and (3
-1) to (3-27), a polymer obtained by polymerizing the monomers alone, these monomers and (4-1)
) To (4-10) monomers and the polymers (5-1) to (5-55) described above as specific examples have a weight average molecular weight of 700 to 1,000,000, preferably 700 to 500,000, more preferably 900 to 300,000.

The resist underlayer film forming composition of the present invention can change the content (% by mass) of halogen atoms contained in the polymer compound in the composition. That is, selection of the main chain structure of the polymer compound, selection of the type of unit monomer used for the synthesis of the polymer compound, selection of the type of compound to be reacted with the polymer obtained by the polymerization reaction, the number and types of halogen atoms contained By selecting, it is possible to change the content (% by mass) of the halogen atom contained in the polymer compound. Then, by using polymer compounds having different halogen atom contents (mass%), the halogen atom content (mass%) in the solid content of the resist underlayer film forming composition, that is, the resist underlayer film after film formation The halogen atom content (% by mass) in the medium can be changed. The attenuation coefficient k value of the resist underlayer film can be adjusted by changing the halogen atom content (% by mass) in the resist underlayer film after film formation. Further, the halogen atom content (% by mass) in the resist underlayer film after film formation can be changed by changing the proportion of the polymer compound having a certain halogen atom content in the solid content, Also by this method, it is possible to adjust the attenuation coefficient k value of the resist underlayer film. Here, the solid content of the resist underlayer film forming composition is a component obtained by removing the solvent component from the resist underlayer film forming composition, and the halogen atom content in the resist underlayer film after film formation ( Mass%) is the halogen atom content (mass%) in the solid content of the resist underlayer film forming composition.

The resist underlayer film forming composition of the present invention is preferably crosslinked by heating after application in order to prevent intermixing with the resist to be overcoated, and the resist underlayer film forming composition of the present invention further contains a crosslinker component. Can do. Examples of the cross-linking agent include melamine compounds and substituted urea compounds having a cross-linking substituent such as a methylol group and a methoxymethyl group, and polymer compounds containing an epoxy group. Preferably, it is a cross-linking agent having at least two cross-linking substituents, and is a compound such as methoxymethylated glycouril or methoxymethylated melamine, particularly preferably tetramethoxymethylglycoluril or hexamethoxymethylolmelamine. is there. The addition amount of the crosslinking agent varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 20% by mass with respect to 100% by mass of the total composition. , Preferably 0.01
It is 15 mass%, More preferably, it is 0.05-10 mass%. These crosslinking agents may cause a crosslinking reaction due to self-condensation. However, when a crosslinking-forming substituent is present in the polymer compound used in the resist underlayer film forming composition of the present invention, these crosslinking-forming substituents are present. And can cause a crosslinking reaction.
The polymer compound having a repeating unit structure containing a halogen atom used in the resist underlayer film forming composition for a mask blank of the present invention contains a repeating unit structure containing a halogen atom in the main chain and a halogen atom in the side chain. It consists of a repeating unit structure or a combination thereof.

Preferred examples of the polymer compound having a repeating unit structure containing a halogen atom include compounds represented by the following general formulas (d), (e) and (f).
(In the formula, A is a phenyl group, a naphthyl group, an anthranyl group, a benzoyl group, a naphthylcarbonyl group or an anthranylcarbonyl group (the phenyl group, naphthyl group, anthranyl group, benzoyl group, naphthylcarbonyl group and anthranylcarbonyl group are a hydroxyl group) , Optionally substituted with a halogen atom or both a hydroxyl group and a halogen atom).
Means an integer from 1 to 3000, n means an integer from 0 to 3, and the compound contains at least one halogen atom in the repeating unit. )
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, Preferably a bromine atom or an iodine atom is mentioned.
Preferable A is a benzoyl group, a naphthyl group, or a naphthylcarbonyl group (the benzoyl group, naphthyl group, and naphthylcarbonyl group may be optionally substituted with a hydroxyl group, a halogen atom, or both a hydroxyl group and a halogen atom). Benzoyl group, 1,6-dibromo-2-naphthyl group, 2-naphthylcarbonyl group, 4-hydroxybenzoyl group, 3,5-diiodo-2-hydroxybenzoyl group, 3,5-dibromobenzoyl group 3,5-dibromo-2-hydroxybenzoyl group.
(In the formula, Ar ² and Ar ³ are not the same, and each represents a phenyl group, a naphthyl group or an anthranyl group (the phenyl group, naphthyl group and anthranyl group can be arbitrarily selected from a hydroxyl group, a halogen atom or both a hydroxyl group and a halogen atom) Q and r are each an integer of 1 or more and q + r is an integer of 2 to 3000, n is an integer of 0 to 3, The compound contains at least one halogen atom in the repeating unit containing the substituent Ar ² , contains at least one halogen atom in the repeating unit containing the substituent Ar ³ , or contains the substituent Ar ² (At least one halogen atom is contained in both the repeating unit containing and the repeating unit containing the substituent Ar ^3. )
Preferable Ar ² includes a naphthyl group and a 2-naphthyl group. Preferable Ar ³ includes an anthranyl group and a 9-anthranyl group.
(Wherein R ¹ represents a hydrogen atom or a C _1-4 alkyl group, R ² represents CF ₃ , CCl ₃ , CBr ₃ , CH (OH) CH ₂ OR ³ (wherein R ³ represents a phenyl group) , Naphthyl group or anthranyl group (
The phenyl group, naphthyl group and anthranyl group may be optionally substituted with a hydroxyl group, a halogen atom, or both a hydroxyl group and a halogen atom. ). ) Or CH (OH) CH ₂ OC (O) R ⁴ (wherein R ⁴ is a phenyl group, a naphthyl group or an anthranyl group (the phenyl group, naphthyl group and anthranyl group are a hydroxyl group, a halogen atom or a hydroxyl group and a halogen) Optionally substituted at both of the atoms))), q and r are each an integer of 1 or more and q + r is an integer from 2 to 3000; Contains at least one halogen atom in the repeating unit containing the substituent R ² . )
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
_{Examples of the} C _1-4 alkyl group include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group, and a methyl group is preferable.
Preferable R ¹ includes a hydrogen atom or a methyl group.
Preferable R ³ includes a naphthyl group (the naphthyl group may be optionally substituted with a hydroxyl group, a halogen atom, or both a hydroxyl group and a halogen atom), and 1,6-dibromo-2- A naphthyl group is mentioned.
Preferable R ⁴ includes a phenyl group (the phenyl group may be optionally substituted with a hydroxyl group, a halogen atom, or both a hydroxyl group and a halogen atom), and 3,5-diiodo-2- A hydroxyphenyl group is mentioned.

  As a catalyst for promoting the crosslinking reaction, acidic compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, and / or In addition, a thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate can be blended. The blending amount is 0.02 to 10% by mass, preferably 0.04 to 5% by mass, per 100% by mass of the total solid content.

  In the resist underlayer film forming composition of the present invention, an acid generator can be added in order to match the acidity with the resist coated on the upper layer in the lithography process. Preferred acid generators include, for example, onium salt acid generators such as bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, and phenyl-bis (trichloromethyl) -s-triazine. And halogen-containing compound acid generators such as benzoin tosylate and sulfonic acid acid generators such as N-hydroxysuccinimide trifluoromethanesulfonate. The amount of the acid generator added is 0.02 to 3% by mass, preferably 0.04 to 2% by mass, per 100% by mass of the total solid content.

  To the resist underlayer film forming composition of the present invention, in addition to the above, further rheology adjusting agents, adhesion assistants, surfactants and the like can be added as necessary.

  The rheology modifier is added mainly for the purpose of improving the fluidity of the resist underlayer film forming composition. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate, adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate, Mention may be made of maleic acid derivatives such as normal butyl maleate, diethyl maleate and dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate and tetrahydrofurfuryl oleate, or stearic acid derivatives such as normal butyl stearate and glyceryl stearate. it can. These rheology modifiers are usually blended at a ratio of less than 30% by mass with respect to 100% by mass of the total composition of the resist underlayer film forming composition.

The adhesion assistant is added mainly for the purpose of improving the adhesion between the substrate or the resist and the resist underlayer film forming composition, and preventing the resist from peeling particularly during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, Alkoxysilanes such as enyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsiline) urea, silazanes such as dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ -Silanes such as aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole , Indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc., 1,1-dimethylurea, 1,3-dimethylurea, etc. And urea or thiourea compounds. These adhesion assistants are usually blended at a ratio of less than 5% by mass, preferably less than 2% by mass with respect to 100% by mass of the total composition of the resist underlayer film forming composition.

  In the resist underlayer film forming composition of the present invention, a surfactant can be blended in order to further improve the applicability to surface unevenness without generating pinholes or installations. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, 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 Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sol Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, EFTTOP EF301, EF303, EF352 (Manufactured by Tochem Products Co., Ltd.), Megafuk F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, Fluorosurfactants such as SC103, SC104, SC105, and SC106 (Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), and the like can be mentioned. The compounding amount of these surfactants is usually 0.2% by mass or less, preferably 0.1% by mass or less per 100% by mass of the total composition of the resist underlayer film forming composition of the present invention. These surfactants may be added alone or in combination of two or more.

Solvents for dissolving the polymer include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl 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-methoxypro Use of methyl onate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc. it can. These organic solvents are used alone or in combination of two or more.

  Furthermore, high boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate can be mixed and used. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferable for improving the leveling property.

  As the resist applied to the upper layer of the resist underlayer film in the present invention, either a negative type or a positive type can be used. Chemically amplified resist comprising a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist A chemically amplified resist comprising a binder having a group that changes the alkali dissolution rate by being decomposed by an acid generator and an acid, and a chemically amplified resist comprising a low molecular weight compound that is decomposed by an acid to change the alkaline dissolution rate of the resist There is. In addition, non-chemically amplified resists composed of binders having groups that decompose by electron beams to change the alkali dissolution rate, non-chemically amplified resists composed of binders having sites that are cut by electron beams to change alkali dissolution rates, etc. is there.

  As a developer for a positive resist having a resist underlayer film formed using the resist underlayer film forming composition of the present invention, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia Inorganic amines such as 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 Alcohol amines such as alcohol amines, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine, and alkaline aqueous solutions such as these can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution. Of these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.

  The resist underlayer film produced from the composition for forming a resist underlayer film containing a polymer compound having a repeating unit structure containing a halogen atom according to the present invention has a relatively large dry etching rate because it contains a halogen atom. Moreover, the dry etching rate can be adjusted by changing the content of halogen atoms.

The mask blank to which the resist underlayer film forming composition of the present invention is applied has the following configuration.
(Configuration 1) A mask blank on which a chemically amplified resist film is formed includes a substrate, a thin film that forms a transfer pattern formed on the substrate, and a resist underlayer film formed in this order. It is assumed that a resist underlayer film forming composition containing a polymer compound having a repeating unit structure containing a solvent and a solvent is applied to a thin film forming the transfer pattern and heat-treated. Such a resist underlayer film can reduce the film thickness for obtaining the deactivation suppression effect of the chemically amplified resist film and has a high etching rate, so that the chemical resist layer film is chemically etched while the resist underlayer film is being etched. The amplification resist film is not substantially etched. Therefore, the thin film forming the transfer pattern can be etched while maintaining the resolution of the resist pattern immediately after the formation. Thereby, the resolution of the patterning of the thin film which forms a transfer pattern can be improved.

  The chemically amplified resist film is, for example, a resist function in which an acid of a catalyst substance generated in a resist film by an electron beam reacts with a functional group or a functional substance that suppresses polymer solubility in a subsequent heat treatment step. It is a resist film which expresses. The expression of the resist function means, for example, that the resist function is dissolved by removing a functional group or the like. The chemically amplified resist film is preferably resist-drawn (exposed) with an electron beam accelerated at an acceleration voltage of 50 keV or higher.

  The thickness of the resist underlayer film is 25 nm or less, and when the thin film forming the transfer pattern is etched using the patterned chemically amplified resist as a mask, the etching rate of the resist underlayer film is 1 of the etching rate of the chemically amplified resist film. It is desirable to make it 0.0 times or more, preferably 1.1 to 10 times.

  If the resist underlayer film is thick (for example, 30 nm or more) or a resist underlayer film having a low etching rate is formed, the resist film is also etched while the resist underlayer film is being etched. This is not desirable because the resist underlayer film becomes an obstacle to improving the resolution of the thin film forming the film.

  (Structure 2) The resist underlayer film obtained by the present invention can exhibit a sufficient resist film deactivation suppressing function with an extremely thin film thickness of, for example, about 5 nm. In addition, the etching rate can be appropriately increased. Therefore, a resist underlayer film having an extremely thin thickness and a high etching rate can be formed.

  (Configuration 3) In the present invention, used for a mask blank on which a chemically amplified resist film is formed, suppresses deactivation of the substrate, a thin film that forms a transfer pattern formed on the substrate, and the chemically amplified resist film. And a resist underlayer film formed on a thin film for forming a transfer pattern. If comprised in this way, an extremely thin resist underlayer film with a high etching rate can be formed. Moreover, the resolution of the patterning of the thin film which forms a transfer pattern by this can be improved.

  (Structure 4) In the mask blank to which the resist underlayer film forming composition of the present invention is applied, the thin film forming the transfer pattern is suitable when it is made of a material containing chromium. Specifically, the thin film forming the transfer pattern is a light-shielding film that blocks exposure light, and the light-shielding film includes at least a lower layer mainly composed of chromium carbide (CrC), and chromium oxide or chromium nitride. And an upper layer having an antireflection function containing at least one of the above as a main component. The antireflection layer is, for example, a film obtained by adding oxygen and nitrogen to chromium (CrON film). The antireflection layer may be a film mainly composed of chromium oxide (CrO). Moreover, you may further have the layer which has chromium nitride (CrN) as a main component under the layer which has chromium carbide as a main component.

  When a chromium-based light-shielding film is used as a thin film for forming a transfer pattern, the light-shielding film is dry etched using, for example, a chlorine-based gas or a fluorine-based gas. In this case, if the thickness of the resist underlayer film is large or the etching rate is low, the resist film is etched while the resist underlayer film is being etched, and the resolution of the resist pattern is lowered. However, if (Structure 4) is used, it is possible to appropriately prevent the resolution of the resist pattern from being lowered by dry etching of the chromium-based light-shielding film by using a thin resist underlayer film having a high etching rate. it can.

(Structure 5) A mask blank to which the present invention is applied includes a silicide film formed under a resist underlayer film, and the adhesion of the resist underlayer film to the silicide film is formed by forming a chemically amplified resist film on the silicide film. This is higher than the adhesion of the chemically amplified resist film to the silicide film. With this configuration, the adhesion between the silicide film and the chemically amplified resist film can be improved. Therefore, a chemically amplified resist film can be appropriately formed on the silicide film. This silicide film is a film used as a hard mask, for example. If comprised in this way, a chemically amplified resist film can be used appropriately in a hard mask blank.

  Here, in order to improve the adhesion between the silicide film and the chemically amplified resist film, for example, pretreatment with a silane coupling agent (HMDS or the like) may be considered. However, if such pretreatment is performed, an increase in the number of steps will lead to an increase in cost. On the other hand, according to (Configuration 5), the adhesion between the silicide film and the chemically amplified resist film can be improved by using the resist underlayer film. Therefore, the cost of the mask blank can be reduced without increasing the number of steps for improving the adhesion.

(Configuration 6) The present invention is applied to a mask blank on which a chemically amplified resist film is formed, and is formed on a substrate, a thin film that forms a transfer pattern formed on the substrate, and a thin film that forms a transfer pattern. And a resist underlayer film according to the present invention formed on the silicide film, and the chemically amplified resist film is formed on the underlayer film.
The adhesion of the lower layer film to the silicide film is higher than the adhesion of the chemically amplified resist film to the silicide film when the chemically amplified resist film is formed on the silicide film, and the film thickness of the lower layer film is 25 nm or less. It is.

  When the silicide film is etched using the patterned chemically amplified resist film as a mask, the etching rate of the lower layer film is 1.0 times or more that of the chemically amplified resist film. In this way, the adhesion between the silicide film and the chemically amplified resist film can be improved appropriately. Further, the resolution of the patterning of the silicide film can be appropriately improved.

(Configuration 7) The present invention is applied to a mask blank on which a chemically amplified resist film is formed, and includes a substrate, a silicide film formed on the substrate, and a resist underlayer film according to the present invention formed on the silicide film. The chemically amplified resist film is formed on the lower layer film. In this way, the adhesion between the silicide film and the chemically amplified resist film can be improved appropriately. Further, the resolution of the patterning of the silicide film can be appropriately improved.

  (Configuration 8) A mask blank to which the present invention is applied includes a chemically amplified resist film. If comprised in this way, the developability of the patterning of the thin film or silicide film | membrane which forms a transfer pattern can be improved appropriately. Further, the deactivation of the chemically amplified resist film can be appropriately suppressed.

  (Configuration 9) A mask having a mask pattern formed by patterning a thin film for forming a transfer pattern in the mask blank according to any one of Configurations 1 to 8 can be manufactured. With this configuration, the effects of (Configuration 1) to (Configuration 8) can be obtained.

  In the above, the mask blank includes a transmissive mask blank such as a photomask blank and a phase shift mask blank, and a reflective mask blank. The mask blank includes a blank with a resist film and a blank before forming a resist film.

The phase shift mask blank includes a case where a light-shielding film such as a chromium-based material is formed on the halftone film. In this case, the thin film forming the transfer pattern indicates a halftone film or a light-shielding film. The mask includes a transmissive mask such as a photomask and a phase shift mask, and a reflective mask. The mask includes a reticle.
A reflective mask blank has a configuration in which a multilayer reflective film and an absorber film are formed on a substrate, and a configuration in which a multilayer reflective film, a buffer layer, and an absorber film are formed on a substrate. In this case, a transfer pattern The thin film that forms a film refers to an absorber film, or an absorber film and a buffer layer.

Further, the light shielding film specifically includes a light shielding film that blocks exposure light. The film material, film structure, film thickness, etc. of the light shielding film are not particularly limited. As a film material of the light-shielding film, for example, chromium alone, a material containing at least one element composed of oxygen, nitrogen and carbon in chromium (material containing Cr), or LEAR (Low Energy Activation Resision)
t) When a chemically amplified resist film such as an acetal resist for SEAR or a SCAP resist for HEAR (High Energy Activation Resist) is used, a film material or the like on which a skirt-like protrusion is formed at the bottom of the resist pattern Is mentioned.

  The film composition of the light-shielding film is appropriately adjusted according to optical characteristics (for a photomask blank, optical density, reflectance, etc.). As the film structure of the light-shielding film, a single-layer or multi-layer structure made of the above film materials can be used. Further, in different compositions, a multi-layer structure formed stepwise or a film structure in which the composition is continuously changed can be used. The film thickness of the light-shielding film is appropriately adjusted according to optical characteristics (such as optical density in the case of a photomask blank). In the case of a photomask blank, the thickness of the light shielding film is, for example, 30 to 150 nm.

  According to the present invention, when a chemically amplified resist film is used for a mask blank, the resolution of patterning of a thin film for forming a transfer pattern can be improved. In addition, when a silicide film is used for the base layer of the chemically amplified resist film, the adhesion between the silicide film and the chemically amplified resist film can be improved.

Hereinafter, an embodiment relating to a mask blank to which the resist underlayer film forming composition of the present invention is applied will be described with reference to the drawings.
FIG. 1 is a diagram showing an example of a configuration relating to a first embodiment of a mask blank 10 to which a resist underlayer film forming composition of the present invention is applied. In this example, the mask blank 10 is a mask blank for a binary mask, and includes a transparent substrate 12, a light shielding film 13 (light shielding layer 14, antireflection layer 16), a resist underlayer film 18, and a chemically amplified resist film 20. .

  The transparent substrate 12 is formed of, for example, a quartz substrate or soda lime glass. The light shielding layer 14 has a chromium nitride film 22 and a chromium carbide film 24 in this order on the transparent substrate 12. The chromium nitride film 22 is a layer containing chromium nitride (CrN) as a main component, and has a film thickness of 15 to 20 nm, for example. The chromium carbide film 24 is a layer mainly composed of chromium carbide (CrC), and has a film thickness of, for example, 50 to 60 nm.

  The antireflection layer 16 is a film obtained by adding oxygen and nitrogen to chromium (CrON film), and is formed on the chromium carbide film 24. The film thickness of the antireflection layer 16 is, for example, 20 to 30 nm. The antireflection layer 16 may be a film mainly composed of chromium oxide (CrO).

  The resist underlayer film 18 is a layer for suppressing the deactivation of the chemically amplified resist film 20 and is formed on the light shielding film 13 with the antireflection layer 16 interposed therebetween. The film thickness of the resist underlayer film 18 is, for example, 25 nm or less. The film thickness of the resist underlayer film 18 may be 1 to 25 nm. More preferably, it is 1-15 nm, More preferably, it is 5-10 nm.

  In this example, the resist underlayer film 18 can exhibit a sufficient deactivation suppressing function with a very thin film thickness. In addition, the etching rate can be appropriately increased. A chemically amplified resist film 20 is formed on the resist underlayer film 18.

  In addition, in the modification concerning 1st Embodiment of the mask blank 10 to which the resist underlayer film forming composition of this invention is applied, the mask blank 10 may be a mask blank for phase shift. In this case, the mask blank 10 further includes a phase shift film, for example, between the transparent substrate 12 and the light shielding film 13. As the phase shift film, for example, various known halftone films such as chromium (CrON, etc.), molybdenum (MoSiON, etc.), tungsten (WSiON, etc.), and silicon (SiN, etc.) can be used. The phase shift mask blank 10 may include a phase shift film on the antireflection layer 16.

  FIG. 2 shows a state in which the chemically amplified resist film 20 in the first embodiment of the mask blank 10 to which the resist underlayer film forming composition of the present invention is applied is patterned by an electron beam lithography method. Using the patterned chemically amplified resist film 20 as a mask, the resist underlayer film 18 and the light-shielding film 13 (the antireflection layer 16 and the light-shielding layer 14) are etched, thereby patterning the light-shielding film 13. A mask can be manufactured. This photomask includes a light-shielding film pattern formed by patterning.

  The conditions for etching the light-shielding film 13 are the etching conditions in the step of etching the light-shielding film 13 using the patterned chemically amplified resist film 20 as a mask.

  In this case, under this etching condition, the etching rate of the resist underlayer film 18 is 1.0 times or more with respect to the etching rate (etching rate) at which the chemically amplified resist film 20 used as a mask is etched. Therefore, according to this example, the light-shielding film 13 can be etched without reducing the resolution of the chemically amplified resist film 20. Thereby, the resolution of patterning of the light-shielding film 13 can be improved. The etching rate of the resist underlayer film is, for example, 1.0 to 20 times the etching rate of the chemically amplified resist film 20. More preferably, it is 1.0-10 times, More preferably, it is 1.1-10 times.

Synthesis example 1
(Synthesis of polymer compound of formula [5-42])
Brominated epoxyphenol novolak resin (produced by Nippon Kayaku Co., Ltd., trade name BREN-304, bromine atom content 42% by mass, having about 1.5 bromine atoms per benzene ring) and benzoic acid 11 .6 g was dissolved in 168.4 g of propylene glycol monomethyl ether, 0.56 g of benzyltriethylammonium was added, and the mixture was reacted at reflux temperature for 24 hours to obtain a polymer compound solution of [5-42]. When the GPC analysis of the obtained high molecular compound was conducted, the weight average molecular weight was 2500 in standard polystyrene conversion.

Synthesis example 2
(Synthesis of polymer compound of formula [5-43])
Brominated epoxyphenol novolak resin (Nippon Kayaku Co., Ltd., trade name BREN-304, bromine atom content 42% by mass, having about 1.5 bromine atoms per benzene ring) 30.0 g, 2-naphthalene After dissolving 6.5 g of carboxylic acid and 12.6 g of 9-anthracenecarboxylic acid in 198.7 g of propylene glycol monomethyl ether, 0.56 g of benzyltriethylammonium was added and reacted at reflux temperature for 24 hours. A solution of the polymer compound was obtained. When the GPC analysis of the obtained high molecular compound was conducted, the weight average molecular weight was 2800 in standard polystyrene conversion.

Synthesis example 3
(Synthesis of polymer compound of formula [5-44])
Brominated epoxyphenol novolak resin (Nippon Kayaku Co., Ltd., trade name BREN-304, bromine atom content 42 mass%, having about 1.5 bromine atoms per benzene ring) 30.0 g and 1,6 -After dissolving 27.0 g of dibromo-2-naphthol in 231.3 g of propylene glycol monomethyl ether, 0.84 g of benzyltriethylammonium was added and reacted at reflux temperature for 24 hours to obtain a polymer compound of the formula [5-44] A solution was obtained. When the GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 2700 in standard polystyrene conversion.

Synthesis example 4
(Synthesis of polymer compound of formula [5-45])
Brominated epoxyphenol novolak resin (Nippon Kayaku Co., Ltd., trade name BREN-304, bromine atom content 42% by mass, having about 1.5 bromine atoms per benzene ring) 30.0 g and 2-naphthalene After dissolving 16.3 g of carboxylic acid in 187.3 g of propylene glycol monomethyl ether, 0.56 g of benzyltriethylammonium was added and reacted at reflux temperature for 24 hours to obtain a solution of the polymer compound of the formula [5-45]. . When the GPC analysis of the obtained high molecular compound was conducted, the weight average molecular weight was 3000 in standard polystyrene conversion.

Synthesis example 5
(Synthesis of polymer compound of formula [5-46])
Brominated epoxyphenol novolak resin (Nippon Kayaku Co., Ltd., trade name BREN-304, bromine atom content 42% by mass, about 1.5 bromine atoms per benzene ring) 30.0 g and 4-hydroxy After dissolving 12.3 g of benzoic acid in 171.6 g of propylene glycol monomethyl ether, 0.56 g of benzyltriethylammonium was added and reacted at reflux temperature for 24 hours to obtain a solution of the polymer compound of the formula [5-46]. . When the GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 3200 in standard polystyrene conversion.

Synthesis Example 6
(Synthesis of polymer compound of formula [5-47])
Brominated epoxyphenol novolac resin (Nippon Kayaku Co., Ltd., trade name BREN-304, bromine atom content 42 mass%, having about 1.5 bromine atoms per benzene ring) 30.0 g and 3,5 -After dissolving 34.8 g of diiodosalicylic acid in 262.7 g of propylene glycol monomethyl ether, 0.84 g of benzyltriethylammonium was added and reacted at reflux temperature for 24 hours to obtain a solution of the polymer compound of the formula [5-47]. Obtained. When the GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 3400 in standard polystyrene conversion.

Synthesis example 7
(Synthesis of polymer compound of formula [5-48])
After dissolving 21 g of glycidyl methacrylate and 39 g of 2-hydroxypropyl methacrylate in 242 g of propylene glycol monomethyl ether, the temperature was raised to 70 ° C. Thereafter, 0.6 g of azobisisobutyronitrile was added while maintaining the reaction solution at 70 ° C., and the mixture was reacted at 70 ° C. for 24 hours to obtain a polymer solution. When GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 50000 in standard polystyrene conversion.
To 100 g of a solution containing 20 g of this resin, 13 g of 1,6-dibromo-2-naphthol, 0.3 g of benzyltriethylammonium chloride and 454 g of propylene glycol monomethyl ether were added and reacted at 130 ° C. for 24 hours to obtain the formula [5-48]. A solution of the polymer compound was obtained.

Synthesis example 8
(Synthesis of polymer compound of formula [5-49])
After dissolving 21 g of glycidyl methacrylate and 39 g of 2-hydroxypropyl methacrylate in 242 g of propylene glycol monomethyl ether, the temperature was raised to 70 ° C. Thereafter, 0.6 g of azobisisobutyronitrile was added while maintaining the reaction solution at 70 ° C., and the mixture was reacted at 70 ° C. for 24 hours to obtain a polymer solution. When GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 50000 in standard polystyrene conversion.
To 100 g of a solution containing 20 g of this resin, 17 g of 3,5-diiodosalicylic acid, 0.3 g of benzyltriethylammonium chloride and 469 g of propylene glycol monomethyl ether are added and reacted at 130 ° C. for 24 hours to increase the amount of the formula [5-49]. A solution of molecular compounds was obtained.

Synthesis Example 9
(Synthesis of polymer compound of formula [5-50])
After dissolving 5.0 g of 2-hydroxyethyl methacrylate and 25.8 g of trifluoroethyl methacrylate in 123.3 g of propylene glycol monomethyl ether, the temperature was raised to 70 ° C. Thereafter, 0.3 g of azobisisobutyronitrile was added while maintaining the reaction solution at 70 ° C., and the mixture was reacted at 70 ° C. for 24 hours to obtain a solution of the polymer compound of the formula [5-50]. When the GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 52000 in standard polystyrene conversion.

Synthesis Example 10
(Synthesis of polymer compound of formula [5-51])
After dissolving 5.0 g of 2-hydroxyethyl methacrylate and 33.4 g of tolchloroethyl methacrylate in 153.7 g of propylene glycol monomethyl ether, the temperature was raised to 70 ° C. Thereafter, 0.4 g of azobisisobutyronitrile was added while maintaining the reaction solution at 70 ° C., and the mixture was reacted at 70 ° C. for 24 hours to obtain a solution of the polymer compound of the formula [5-51]. When GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 47000 in standard polystyrene conversion.

Synthesis Example 11
(Synthesis of polymer compound of formula [5-52])
After dissolving 5.0 g of 2-hydroxyethyl methacrylate and 53.9 g of tolbromoethyl methacrylate in 235.7 g of propylene glycol monomethyl ether, the temperature was raised to 70 ° C. Thereafter, 0.6 g of azobisisobutyronitrile was added while maintaining the reaction solution at 70 ° C., and the mixture was reacted at 70 ° C. for 24 hours to obtain a solution of the polymer compound of the formula [5-52]. When the GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 51000 in standard polystyrene conversion.

Synthesis Example 12
(Synthesis of polymer compound of formula [5-53])
After dissolving 30.0 g of epoxidized phenol novolac resin and 40.4 g of 3,5-dibromobenzoic acid in 285.3 g of propylene glycol monomethyl ether, 0.91 g of benzyltriethylammonium was added and reacted at reflux temperature for 24 hours. A solution of the polymer compound [5-53] was obtained. When the GPC analysis of the obtained high molecular compound was conducted, the weight average molecular weight was 1800 in standard polystyrene conversion.

Synthesis Example 13
(Synthesis of polymer compound of formula [5-54])
30.0 g of epoxidized phenol novolak resin and 42.7 of 3,5-dibromosalicylic acid
g was dissolved in 294.5 g of propylene glycol monomethyl ether, 0.91 g of benzyltriethylammonium was added, and the mixture was reacted at reflux temperature for 24 hours to obtain a solution of the polymer compound of the formula [5-54]. When the GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 1900 in standard polystyrene conversion.

Synthesis Example 14
(Synthesis of polymer compound of formula [5-55])
After dissolving 30.0 g of epoxidized phenol novolac resin and 37.5 g of 3,5-diiodosalicylic acid in 232.5 g of propylene glycol monomethyl ether, 0.61 g of benzyltriethylammonium was added and reacted at reflux temperature for 24 hours. A solution of the polymer compound [5-55] was obtained. When the GPC analysis of the obtained high molecular compound was performed, the weight average molecular weight was 2200 in standard polystyrene conversion.

Example 1
10 g of a propylene glycol monomethyl ether solution containing 2 g of the polymer compound obtained in Synthesis Example 1 above, 0.5 g of tetrabutoxymethylglycoluril, 0.01 g of p-toluenesulfonic acid, 0.04 g of pyridinium p-toluenesulfonic acid, and megafac 0.004 g of R-30 (surfactant, manufactured by Dainippon Ink Co., Ltd.) was mixed and dissolved in 49.8 g of propylene glycol monomethyl ether, 16.5 g of propylene glycol monomethyl ether acetate and 8.3 g of cyclohexanone to obtain a solution. . Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with a hole diameter of 0.05 micrometer, and prepared the resist underlayer film forming composition.

Example 2
A composition of Example 2 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 2.

Example 3
A composition of Example 3 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 3.

Example 4
A composition of Example 4 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 4.

Example 5
A composition of Example 5 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 5.

Example 6
A composition of Example 6 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 6.

Example 7
A composition of Example 7 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 7.

Example 8
A composition of Example 8 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 8.

Example 9
A composition of Example 9 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 9.

Example 10
A composition of Example 10 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 10.

Example 11
A composition of Example 11 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 11.

Example 12
A composition of Example 12 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 12.

Example 13
A composition of Example 13 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 13.

Example 14
A composition of Example 14 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 14.

Example 15
A composition of Example 15 was obtained in the same manner as in Example 1 except that tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine.

Example 16
The composition of Example 16, except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 2 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine Got.

Example 17
The composition of Example 17 was repeated except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 3 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

Example 18
The composition of Example 18 was prepared in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 4 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

Example 19
The composition of Example 19 was carried out in the same manner as in Example 1, except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 5 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

Example 20
The composition of Example 20 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 6 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

Example 21
The composition of Example 22, except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 7 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine Got.

Example 22
The composition of Example 22, except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 8 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine Got.

Example 23
The composition of Example 23 was obtained in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 9 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

Example 24
The composition of Example 24 was prepared in the same manner as in Example 1, except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 10 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

Example 25
The composition of Example 25 was carried out in the same manner as in Example 1, except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 11 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

Example 26
The composition of Example 26 was carried out in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 12 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

Example 27
The composition of Example 27 was prepared in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 13 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

Example 28
The composition of Example 28 was carried out in the same manner as in Example 1 except that the polymer compound of Synthesis Example 1 was changed to the polymer compound of Synthesis Example 14 and tetrabutoxymethylglycoluril was changed to hexamethoxymethylolmelamine. Got.

(Elution test for resist solvent)
The resist underlayer film forming composition prepared in Examples 1 to 28 was applied onto a silicon wafer using a spinner. It was heated at 205 ° C. for 1 minute on a hot plate to form a resist underlayer film (film thickness: 0.10 μm). This resist underlayer film was immersed in a solvent used for the resist, such as ethyl lactate and propylene glycol monomethyl ether, and confirmed to be insoluble in the solvent.

(Measurement of dry etching rate)
The resist underlayer film forming composition prepared in Examples 1 to 28 was applied onto a silicon wafer using a spinner. It was heated at 205 ° C. for 1 minute on a hot plate to form a resist underlayer film (film thickness: 0.10 μm). The dry etching rate was measured using a RIE system ES401 manufactured by Nippon Scientific.

  Similarly, a resist film was formed on a silicon wafer using a spinner. And the dry etching rate was measured using the RIE system ES401 made from Japan Scientific, and it compared with the dry etching rate of the resist underlayer film of Examples 1-28. The results are shown in Table 1.

In Table 1, the dry etching rate ratio (resist underlayer film / resist) of the coating type underlayer film of the present invention with respect to the resist was measured using CF ₄ gas as an etching gas.
[Table 1] Dry etching rate ratio (resist underlayer film / resist film)
―――――――――――――――――――――――――――――――
Example 1 1.3
Example 2 1.3
Example 3 1.5
Example 4 1.3
Example 5 1.5
Example 6 1.7
Example 7 1.5
Example 8 1.7
Example 9 2.3
Example 10 2.7
Example 11 3.2
Example 12 1.3
Example 13 1.5
Example 14 1.5
Example 15 1.3
Example 16 1.3
Example 17 1.5
Example 18 1.3
Example 19 1.5
Example 20 1.7
Example 21 1.5
Example 22 1.7
Example 23 2.3
Example 24 2.7
Example 25 3.2
Example 26 1.3
Example 27 1.5
Example 28 1.5
―――――――――――――――――――――――――――――――

Hereinafter, examples and comparative examples relating to the first embodiment of the mask blank to which the resist underlayer film forming composition of the present invention is applied will be described.
Example 29
A synthetic quartz substrate having a size of 152.4 mm square and a thickness of 6.35 mm is used as the transparent substrate 12, and the light shielding layer 14 is formed by laminating a chromium nitride film 22 and a chromium carbide film 24 as the light shielding film 13 on the transparent substrate 12. Then, a film obtained by adding oxygen and nitrogen to chromium (CrON film) was formed as the antireflection layer 16. The film thickness of the antireflection layer 16 was 30 nm. The film thickness of the chromium nitride film 22 was about 20 nm, and the film thickness of the chromium carbide film 24 was about 60 nm.

  Further, the resist underlayer film forming composition of Example 6 was applied by a spin coating method (spinner method) to a thickness of about 10 nm to form a resist underlayer film 18. Thereafter, the resist underlayer film 18 was dried by heat treatment at 130 ° C. for 10 minutes on a hot plate. Next, as the chemically amplified resist film 20, a commercially available chemical amplified positive resist for electron beam exposure (FEP171: manufactured by Fuji Film Arch Co., Ltd.) is applied at a thickness of about 400 nm by a spin coating method, and then 130 by a hot plate. The chemically amplified resist film 20 was dried by heat treatment at 10 ° C. for 10 minutes to obtain a mask blank 10 that is a photomask blank with a resist film.

Comparative Example 1
A mask blank related to Comparative Example 1 was obtained in the same manner as in Example 29 except that the resist underlayer film 18 was not formed.

Comparative Example 2
A known organic antireflection film (BARC: Bottom Ant) as the resist underlayer film 18
i Reflection Coating: A mask blank relating to Comparative Example 2 was obtained in the same manner as in Example 29 except that an antireflection film containing a polymer compound containing no halogen atom was used. The BARC used was Nissan Chemical Industries, Ltd. (trade name NCA3211).

  For the mask blanks related to Example 29 and Comparative Examples 1 and 2, the light-shielding film was patterned in order to compare the difference in resolution. First, each mask blank was exposed with an electron beam exposure apparatus, and then a baking process and a development process after the exposure were performed to form a resist pattern. This exposure was performed with an electron beam accelerated at an acceleration voltage of 50 eV or more.

Subsequently, the resist underlayer film 18 and the light shielding film 13 (the antireflection layer 16 and the light shielding layer 14) were patterned by dry etching using the resist pattern as a mask and Cl ₄ O ₂ as an etching gas. Note that, under this dry etching condition, the etching rate of the resist underlayer film of Example 29 is about 10 nm / second. Further, the etching rate of the organic antireflection film used instead of the resist underlayer film of Comparative Example 2 is about 5 nm / second, which is lower than that of Example 29.

  FIG. 3 is a cross-sectional photograph of the mask blank 10 according to Example 29 showing the state of the chemically amplified resist film and the light-shielding film after dry etching. In Example 29, it was confirmed that no skirt-like protrusions at the bottom of the resist pattern were formed. Further, it was confirmed that the light-shielding film 13 was patterned without causing a decrease in resolution of the resist pattern.

  The chemically amplified resist film 20 and the resist underlayer film 18 are removed to use the photomask as a photomask to project the protruding portion (with a jagged pattern edge) of the light shielding film 13 (antireflection layer 16 and light shielding layer 14). ), The roughness was about 10 nm or less. It was also confirmed that the 100 nm line and space patterns were resolved. The chemically amplified resist film 20 and the resist underlayer film 18 were removed by immersing them in a resist stripping solution obtained by adding hydrogen peroxide to concentrated sulfuric acid.

  FIG. 4 is a cross-sectional photograph of the mask blank according to Comparative Example 1, showing the state of the chemically amplified resist film and the light-shielding film after dry etching. In Comparative Example 1, it was confirmed that a skirt-like protrusion was formed at the skirt of the resist pattern. Moreover, when the chemically amplified resist film was removed and a photomask was used to examine a protruding portion (with a jagged pattern edge) of the light-shielding film (antireflection layer and light-shielding layer) with a SEM (scanning electron microscope), about The roughness was about 30 nm. In addition, only 200 nm line and space patterns were resolved.

  FIG. 5 is a cross-sectional photograph of a mask blank according to Comparative Example 2, showing the state of the chemically amplified resist film and the light-shielding film after dry etching. In Comparative Example 2, the resolution of the resist pattern was lowered due to the influence of dry etching. Therefore, the chemically amplified resist film and the resist underlayer film are removed, and a photomask is used to examine the protruding portion of the light-shielding film (antireflection layer and light-shielding layer) (with a jagged pattern edge) using a scanning electron microscope (SEM). As a result, the roughness was about 30 nm. In addition, only 200 nm line and space patterns were resolved.

  FIG. 6 is a diagram showing an example of a configuration relating to the second embodiment of the mask blank 10 to which the resist underlayer film forming composition of the present invention is applied. Except for the points described below, in FIG. 6, the same or similar components as those in FIG. 1 are denoted by the same reference numerals as those in FIG. In this example, the mask blank 10 includes a transparent substrate 12, a light shielding film 13 (light shielding layer 14, antireflection layer 16), a silicide film 32, a resist underlayer film 18, and a chemically amplified resist film 20.

The silicide film 32 is a hard mask silicide film and sandwiches the antireflection layer 16 therebetween. Note that the silicide film 32 is a film formed of a silicide-based material. The silicide film 32 may be a film containing MoSi such as MoSiO, MoSiN, or MoSiON, for example. The silicide film may be a film such as TaSiO, TaSiN, TaSiON, WSiO, WSiN, WSiON, ZrSiO, ZrSiN, ZrSiON, TiSiO, TiSiN, or TiSiON.
The resist underlayer film 18 is an organic film for improving the adhesion between the silicide film 32 and the chemically amplified resist film 20, and is formed on the silicide film 32.

  The adhesion of the resist underlayer film 18 to the silicide film 32 is higher than the adhesion of the chemically amplified resist film 20 to the silicide 32 when the chemically amplified resist film 20 is formed on the silicide film 32. The film thickness of the resist underlayer film is, for example, 25 nm or less (for example, 1 to 25 nm). More preferably, it is 1-15 nm, More preferably, it is 5-10 nm. A chemically amplified resist film 20 is formed on the resist underlayer film 18.

FIG. 7 shows a state in which the chemically amplified resist film 20 in the second embodiment of the mask blank 10 to which the resist underlayer film forming composition of the present invention is applied is patterned by an electron beam lithography method. The resist underlayer film 18 and the silicide film 32 are etched using the chemically amplified resist film 20 thus patterned as a mask. Further, the light shielding film 13 (the antireflection layer 16 and the light shielding layer 14) is etched using the silicide film 32 as a mask (hard mask).
Thereby, the photomask which patterned the light-shielding film | membrane 13 can be manufactured.

The conditions for etching the silicide film 32 are the etching conditions in the step of etching the silicide film 32 using the patterned chemically amplified resist film 20 as a mask.
In this case, under this etching condition, the etching rate of the resist underlayer film 18 is 1.0 times or more than the etching rate at which the chemically amplified resist film 20 used as a mask is etched. Therefore, according to this example, the silicide film 32 can be etched without reducing the resolution of the chemically amplified resist film 20. Thereby, the resolution of patterning of the silicide film 32 can be improved. Furthermore, the resolution of the patterning of the silicide film 32 used as a hard mask is enhanced, so that the resolution of the light shielding film 13 can be enhanced. The etching rate of the resist underlayer film 18 is 1.0 to 20 times the etching rate of the chemically amplified resist film 20.
More preferably, it is 1.0 to 20 times, and still more preferably 1.1 to 10 times.

Hereinafter, examples and comparative examples relating to the second embodiment of the mask blank 10 to which the resist underlayer film forming composition of the present invention is applied will be described.
Example 30
Using the same transparent substrate 12 as in Example 29, the light-shielding film 13 (the light-shielding layer 14 and the antireflection layer 16) was formed in the same manner as in Example 29. Further, a MoSiON film was formed as the silicide film 32. The film thickness of the silicide film 32 was 10 nm.
Next, the resist underlayer film forming composition of Example 6 was applied with a film thickness of about 10 nm by a spin coating method (spinner method) to form a resist underlayer film 18. Thereafter, the resist underlayer film 18 was dried by heat treatment at 130 ° C. for 10 minutes on a hot plate. Next, a chemically amplified resist film 20 was formed in the same manner as in Example 29 to obtain a mask blank 10 that is a photomask blank with a resist film.

Comparative Example 3
A mask blank according to Comparative Example 3 was obtained in the same manner as in Example 30 except that the resist underlayer film 18 was not formed.
For the mask blanks according to Example 30 and Comparative Example 3, the chemically amplified resist film was patterned in order to compare the difference in adhesion between the chemically amplified resist film and the silicide film. First, each mask blank was exposed with an electron beam irradiation apparatus, and then a heat treatment and development treatment after exposure were performed to form a resist pattern. This exposure was performed with an electron beam accelerated at an acceleration voltage of 50 eV or more.

  FIG. 8 is a top view photograph of the mask blank 10 according to Example 30, showing the state of the chemically amplified resist film after the development processing. In Example 30, the adhesion between the chemically amplified resist film 20 and the silicide film 32 is improved by the resist underlayer film 18. Therefore, it was confirmed that the desired line and space patterns were firmly formed.

  FIG. 9 is a top view photograph of the mask blank according to Comparative Example 3, showing the state of the chemically amplified resist film after the development processing. In Comparative Example 3, the adhesion between the chemically amplified resist film and the silicide film was insufficient, and the resist pattern disappeared during the development process.

Example 31
A synthetic quartz substrate having a size of 152.4 mm square and a thickness of 6.35 mm is used as the transparent substrate 12, a halftone phase shifter film made of a molybdenum silicide nitride film is formed on the transparent substrate 12, and the light shielding film 13 is further formed. The mask blank and the mask were formed in the same manner as in Example 29 except that the light shielding layer 14 in which the chromium nitride film 22 and the chromium carbide film 24 were laminated and the antireflection layer 16 of chromium oxynitride were formed to produce the mask blank. Obtained. The composition and film thickness of the halftone phase shifter film were adjusted so that the transmittance was 5.5% and the phase shift amount was 180 ° in an ArF excimer laser (wavelength: 193 nm). The film thickness of the light-shielding film 13 was adjusted to 59 nm by adjusting the optical density to be 3.0 or more in the combination of the halftone phase shifter film and the light-shielding film 13.
As a result, the 80 nm line and space pattern was resolved, and the result was that the pattern was more uneven than Example 29.

  As mentioned above, although the mask blank which applies the resist underlayer film forming composition of this invention was demonstrated using embodiment, the technical scope of this invention is not limited to the range described in the said embodiment. Various modifications or improvements can be added to the above embodiment.

  The present invention relates to a resist underlayer film forming composition for forming an underlayer film applied to a mask blank and a mask resist, a mask blank having a resist underlayer film formed of the resist underlayer film forming composition, and the mask blank. A mask made using the method is provided.

FIG. 1 is a cross-sectional view showing a mask blank 10 according to a first embodiment to which the resist underlayer film forming composition of the present invention is applied. FIG. 2 is a cross-sectional view showing an upper portion of the mass blank 10 of FIG. 1 in which the chemically amplified resist film 20 is patterned by the electron beam lithography method. FIG. 3 is a photograph of cross sections of the chemically amplified resist film and the light-shielding film after dry etching of the mask blank 10 according to Example 29. FIG. 4 is a photograph of a cross section of the chemically amplified resist film and the light shielding film after dry etching of the mask blank according to Comparative Example 1. FIG. 5 is a photograph of a cross section of a chemically amplified resist film and a light-shielding film after dry etching of a mask blank according to Comparative Example 2. FIG. 6 is a cross-sectional view showing a mask blank 10 according to a second embodiment to which the resist underlayer film forming composition of the present invention is applied. FIG. 7 is a cross-sectional view showing an upper portion of the mass blank 10 of FIG. 6 in which the chemically amplified resist film 20 is patterned by the electron beam lithography method. FIG. 8 is a photograph of the top surface of the chemically amplified resist film after the development processing of the mask blank 10 according to Example 30. FIG. 9 is a photograph of the upper surface of the chemically amplified resist film after the development of the mask blank according to Comparative Example 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Mask blank 12 Transparent substrate 13 Light-shielding film 14 Light-shielding layer 16 Antireflection layer 18 Resist underlayer film 20 Chemical amplification type resist film 22 Chromium nitride film 24 Chromium carbide film 32 Silicide film

Claims (13)

A resist underlayer film forming composition used for a mask blank formed on a substrate in the order of a thin film for forming a transfer pattern, a resist underlayer film, and a chemically amplified resist film, and having a repeating unit structure containing a halogen atom A resist underlayer film forming composition comprising a polymer compound having a solvent and a solvent. The resist underlayer film forming composition according to claim 1, wherein the polymer compound contains at least 10% by mass of a halogen atom. The polymer compound is represented by the formula (1):
(Wherein, L represents a bonding group constituting the main chain of the polymer compound, M represents a direct bond, or -C (= O) -, - CH 2 - comprises at least one selected or from -O- Q is an organic group, and at least one of L, M, and Q contains a halogen atom, V is the number of unit structures contained in the polymer compound, and is a number from 1 to 3000. The resist underlayer film forming composition according to claim 1, wherein the resist underlayer film forming composition is represented by: The resist underlayer film forming composition according to claim 3, wherein L is a main chain of an acrylic or novolac polymer compound. The resist underlayer film forming composition according to any one of claims 1 to 4, wherein the halogen atom is a chlorine atom, a bromine atom, or an iodine atom. The resist underlayer film forming composition according to any one of claims 1 to 5, wherein the polymer compound and the solvent further contain a crosslinking agent and a crosslinking catalyst. The resist underlayer film forming composition according to any one of claims 1 to 6, wherein the polymer compound and the solvent further contain an acid generator. The resist underlayer film forming composition according to any one of claims 1 to 7, wherein the polymer compound has a weight average molecular weight of 700 to 1,000,000. The resist underlayer film forming composition according to any one of claims 1 to 8, wherein the resist blank film is a mask blank in which a thin film for forming a transfer pattern and a resist underlayer film are sequentially formed on a substrate. A mask blank, which is a resist underlayer film formed from a material. The mask blank according to claim 9, wherein the thin film forming the transfer pattern is made of a material containing chromium. The mask blank is a mask manufacturing method in which a thin film forming the transfer pattern is patterned by dry etching of chlorine-based gas containing chlorine using a resist pattern formed by a chemically amplified resist formed on the resist underlayer film as a mask. The mask blank according to claim 9, wherein the mask blank is a dry etching mask blank corresponding to the above. The mask blank according to claim 9, wherein a chemically amplified resist film is formed on the resist underlayer film. A mask comprising a mask pattern formed by patterning a thin film forming the transfer pattern in the mask blank according to claim 9.