JP6004172B2 - Lithographic resist underlayer film forming composition containing carbonyl group-containing carbazole novolak - Google Patents

Description

  The present invention relates to a resist underlayer film forming composition for lithography containing a carbonyl group-containing carbazole novolak. Furthermore, a resist underlayer film forming composition for lithography effective when processing a semiconductor substrate using a resist underlayer film forming composition for lithography containing a carbonyl group-containing carbazole novolak, and a resist pattern forming method using the resist underlayer film forming composition, and The present invention relates to a method for manufacturing a semiconductor device.

  Conventionally, in the manufacture of semiconductor devices, fine processing by lithography using a photoresist composition has been performed. In the fine processing, a thin film of a photoresist composition is formed on a substrate to be processed such as a silicon wafer, and irradiated with actinic rays such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, and developed. This is a processing method for etching a substrate to be processed such as a silicon wafer using the obtained photoresist pattern as a protective film. However, in recent years, the degree of integration of semiconductor devices has increased, and the actinic rays used tend to be shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm). Accordingly, the influence of diffuse reflection of active rays from the substrate and standing waves has been a serious problem. Therefore, a method of providing an antireflection film (Bottom Anti-Reflective Coating, BARC) between the photoresist and the substrate to be processed has been widely studied.

  In the future, as the miniaturization of the resist pattern proceeds, there arises a problem of resolution and a problem that the resist pattern collapses after development, and it is desired to reduce the thickness of the resist. For this reason, it is difficult to obtain a resist pattern film thickness sufficient for substrate processing, and not only the resist pattern but also the resist underlayer film formed between the resist and the semiconductor substrate to be processed functions as a mask during substrate processing. The process to have it has become necessary. Unlike conventional resist underlayer films with high etch rate (fast etching speed) as resist underlayer films for such processes, compared to resist underlayer films and resists for lithography, which have a selectivity of dry etching rate close to that of resist There has been a demand for a resist underlayer film for lithography having a low dry etching rate selection ratio and a resist underlayer film for lithography having a low dry etching rate selection ratio compared to a semiconductor substrate.

  Examples of the polymer for the resist underlayer film include the following.

  A resist underlayer film forming composition using polyvinyl carbazole is exemplified (see Patent Document 1, Patent Document 2, and Patent Document 3).

  A resist underlayer film forming composition using a fluorenephenol novolak resin is disclosed (for example, see Patent Document 4).

  A resist underlayer film forming composition using a fluorene naphthol novolak resin is disclosed (see, for example, Patent Document 5).

  A resist underlayer film forming composition containing a resin having fluorenephenol and arylalkylene as repeating units is disclosed (see, for example, Patent Document 6 and Patent Document 7).

  A novolak resin using carbazole and aldehyde is disclosed (see Patent Document 8).

JP-A-2-293850 Japanese Patent Laid-Open No. 1-154050 JP-A-2-22657 JP 2005-128509 A JP2007-199653A JP2007-178974 U.S. Pat. No. 7,378,217 International publication pamphlet WO2010 / 147155

  The present invention provides a novel carbazole novolac resin. Furthermore, this invention is providing the resist underlayer film forming composition used for the lithography process of semiconductor device manufacture using a carbazole novolak resin. In addition, the present invention does not cause intermixing with the resist layer, provides an excellent resist pattern, and has a dry etching rate selection ratio close to that of the resist. An object of the present invention is to provide a resist underlayer film for lithography having a ratio and a resist underlayer film for lithography having a low dry etching rate selection ratio as compared with a semiconductor substrate. In addition, the present invention can also provide the ability to effectively absorb the reflected light from the substrate when using irradiation light having a wavelength of 248 nm, 193 nm, 157 nm or the like for fine processing. Furthermore, this invention is providing the formation method of the resist pattern using the resist underlayer film forming composition. And the resist underlayer film forming composition for forming the resist underlayer film which also has heat resistance is provided.

As a first aspect of the present invention, the unit structure of the following formula (1):

(In Formula (1), A represents a structure having carbazole, B represents a structure having an aromatic ring, C represents a structure having a hydrogen atom, an alkyl group or an aromatic ring, and B and C constitute a ring together. A resist containing a polymer having a unit structure represented by 1 to 4 carboxyl groups or salts thereof, or a carboxylic acid ester group in a structure in which A, B, and C are combined. Underlayer film forming composition,
As a second aspect, the unit structure of the above formula (1) is represented by the following formula (2):

(In the formula (2), R ¹ and R ² are each a halogen group, a nitro group, an amino group, a carboxylic acid group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon number. 6 to 40 aryl groups, or a combination thereof, and the alkyl group, the alkenyl group, and the aryl group may include an ether bond, a ketone bond, or an ester bond, and R ³ is a hydrogen atom, An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof, and the alkyl group, the alkenyl group, and the aryl group are ether bonds, It may contain a ketone bond or an ester bond, R ⁴ may be substituted with a halogen group, a nitro group, an amino group or a hydroxy group and has 6 to 6 carbon atoms Represents an aryl group or a heterocyclic group of up to 40, and R ⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group, carbon Represents an aryl group or heterocyclic group of formula 6 to 40, and R ⁴ and R ⁵ may form a ring together with the carbon atom to which they are bonded, R ⁶ is a hydrogen atom, NR ⁰ ₄ Group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof, and the alkyl group, the alkenyl group, and the aryl group are It may contain an ether bond, a ketone bond, or an ester bond, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n1 and n2 each represent an integer of 0 to 3, and n3 represents 1 to Four The resist underlayer film forming composition according to the first aspect, which is an integer),
As a third aspect, the polymer has a unit structure of the above formula (2) and a unit structure of the formula (3):

(In the formula (3), R ⁷ and R ⁸ are each a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 6 to 40 carbon atoms. And the alkyl group, the alkenyl group, or the aryl group may include an ether bond, a ketone bond, or an ester bond, and R ⁹ represents a hydrogen atom or a carbon atom number. An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof, and the alkyl group, the alkenyl group, or the aryl group is an ether bond may also contain a ketone linkage or ester bond .R ¹⁰ is halogen, it may be substituted with a nitro group, an amino group or hydroxy group An aryl group or a heterocyclic group having 6 to 40, R ¹¹ is a hydrogen atom, or a halogen group, a nitro group, an amino group, or optionally substituted by a hydroxy group an alkyl group having 1 to 10 carbon atoms, carbon Represents an aryl group or heterocyclic group of formula 6 to 40, and R ¹⁰ and R ¹¹ may form a ring together with the carbon atom to which they are bonded, and n 4 and n 5 are each 0 to 3 The resist underlayer film-forming composition according to the first aspect, which is a polymer including a polymer including a unit structure represented by a molar ratio of 1 to 99:99 to 1,
As a fourth aspect, R ^3, a resist underlayer film forming composition according to any one of the second aspect or the third aspect R ⁹ is a hydrogen atom of the formula (3) in equation (2),
As a fifth aspect, the resist underlayer film forming composition according to any one of the second aspect to the third aspect, in which the integer n1, the integer n2 in the formula (2), the integer n4 in the formula (3), and the integer n5 are 0 object,
As a sixth aspect, the resist underlayer film forming composition according to any one of the first aspect to the fifth aspect, further including a crosslinking agent,
As a seventh aspect, the resist underlayer film forming composition according to any one of the first aspect to the sixth aspect, further comprising an acid and / or an acid generator,
As an eighth aspect, a resist underlayer film obtained by applying and baking the resist underlayer film forming composition according to any one of the first to seventh aspects on a semiconductor substrate,
As a ninth aspect, the resist underlayer film forming composition according to any one of the first to seventh aspects is applied to a semiconductor substrate and baked to form a lower layer film. Forming a resist pattern;
As a tenth aspect, a step of forming an underlayer film with the resist underlayer film forming composition according to any one of the first to seventh aspects on a semiconductor substrate, a step of forming a resist film thereon, light or A method of manufacturing a semiconductor device, comprising: a step of forming a resist pattern by electron beam irradiation and development; a step of etching the lower layer film with a resist pattern; and a step of processing a semiconductor substrate with a patterned lower layer film;
As an eleventh aspect, a step of forming an underlayer film on the semiconductor substrate with the resist underlayer film forming composition according to any one of the first to seventh aspects, a step of forming a hard mask thereon, and further thereon A step of forming a resist film on the substrate, a step of forming a resist pattern by light and electron beam irradiation and development, a step of etching a hard mask with the resist pattern, a step of etching the lower layer film with a patterned hard mask, and The manufacturing method of the semiconductor device including the process of processing a semiconductor substrate with the patterned underlayer film, and the manufacturing method as described in the 11th viewpoint that a hard mask is by vapor deposition of an inorganic substance as a 12th viewpoint.

With the resist underlayer film forming composition of the present invention, a good resist pattern shape can be formed without causing intermixing between the upper layer portion of the resist underlayer film and the layer coated thereon.

  The resist underlayer film forming composition of the present invention can be imparted with the ability to efficiently suppress reflection from the substrate, and can also have an effect as an antireflection film for exposure light.

  With the resist underlayer film forming composition of the present invention, the dry etching rate selectivity close to the resist, the dry etching rate selectivity lower than that of the resist, and the dry etching rate selectivity lower than that of the semiconductor substrate are excellent. A resist underlayer film can be provided.

  In order to prevent the resist pattern from collapsing after development with the miniaturization of the resist pattern, the resist is thinned. In such a thin film resist, the resist pattern is transferred to the lower layer film by an etching process, the substrate processing is performed using the lower layer film as a mask, or the resist pattern is transferred to the lower layer film by an etching process, and further to the lower layer film. There is a process in which the process of transferring the transferred pattern to the lower layer film using a different gas composition is repeated to finally process the substrate. The resist underlayer film and the composition for forming the resist of the present invention are effective for this process. When a substrate is processed using the resist underlayer film of the present invention, a processed substrate (for example, a thermal silicon oxide film on the substrate, silicon nitride) Film, polysilicon film, etc.) having sufficient etching resistance.

  The resist underlayer film of the present invention can be used as a planarizing film, a resist underlayer film, a resist layer antifouling film, or a film having dry etch selectivity. This makes it possible to easily and accurately form a resist pattern in a lithography process for manufacturing a semiconductor.

  A resist underlayer film by the resist underlayer film forming composition according to the present invention is formed on a substrate, a hard mask is formed thereon, a resist film is formed thereon, a resist pattern is formed by exposure and development, and a resist pattern Is transferred to the hard mask, the resist pattern transferred to the hard mask is transferred to the resist underlayer film, and the semiconductor substrate is processed with the resist underlayer film. In this process, the hard mask may be formed by a coating type composition containing an organic polymer or inorganic polymer and a solvent, or by vacuum deposition of an inorganic substance. In the vacuum deposition of an inorganic material (for example, silicon nitride oxide), the deposited material is deposited on the resist underlayer film surface. At this time, the temperature of the resist underlayer film surface rises to around 400 ° C. In the present invention, since the polymer used is a polymer containing a carbazole novolac-based unit structure, the heat resistance is extremely high, and thermal degradation does not occur even when deposits are deposited.

  This invention is a resist underlayer film forming composition containing the polymer containing the unit structure of Formula (1).

In formula (1), A represents a structure having carbazole, B represents a structure having an aromatic ring, C represents a structure having a hydrogen atom, an alkyl group or an aromatic ring, and B and C constitute a ring together. May be. It has 1 to 4 carboxyl groups or salts thereof, or carboxylic acid ester groups in the structure where A, B and C are combined. The salt of the carboxyl group is preferably an ammonium salt, and examples of the ammonium salt include —NH ₄ , and primary ammonium group, secondary ammonium group, tertiary ammonium group, and quaternary ammonium group.
The resist underlayer film forming composition for lithography of the present invention contains the polymer and a solvent. And it can contain a crosslinking agent and an acid, and can contain additives, such as an acid generator and surfactant, as needed. The solid content of this composition is 0.1 to 70% by mass, or 0.1 to 60% by mass. The solid content is the content ratio of all components excluding the solvent from the resist underlayer film forming composition. The polymer can be contained in the solid content in a proportion of 1 to 100% by mass, or 1 to 99.9% by mass, or 50 to 99.9% by mass.
The polymer used in the present invention has a weight average molecular weight of 600 to 1000000 or 600 to 200000.

  Specific examples of the polymer include a polymer having a unit structure of the formula (2).

In the unit structure of the formula (2), R ¹ and R ² are each a halogen group, a nitro group, an amino group, a carboxylic acid group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, The aryl group has 6 to 40 carbon atoms, or a combination thereof, and the alkyl group, the alkenyl group, and the aryl group may include an ether bond, a ketone bond, or an ester bond. R ³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof, and the alkyl group, the alkenyl group, The aryl group may contain an ether bond, a ketone bond, or an ester bond. R ⁴ represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group or a hydroxy group, and R ⁵ represents a hydrogen atom, a halogen group or a nitro group. Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group which may be substituted with an amino group or a hydroxy group, and R ⁴ and R ⁵ are bonded to each other. And R ⁶ may be a hydrogen atom, NR ⁰ ₄ group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 6 carbon atoms. -40 aryl groups, or a combination thereof, and the alkyl group, the alkenyl group, and the aryl group may include an ether bond, a ketone bond, and an ester bond. R ⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. n1 and n2 are each an integer of 0 to 3. n3 is an integer of 1 to 4.
In the NR ⁰ ₄ group, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include those exemplified below. Specific examples of the NR ⁰ ₄ group include —NH ₄ , and primary ammonium group, secondary ammonium group, tertiary ammonium group, and quaternary ammonium group.

The present invention can use a polymer in which the polymer contains a unit structure of the formula (2) and a unit structure of the formula (3) and has a molar ratio of 1 to 99: 99-1.
In the formula (3), R ⁷ and R ⁸ are each a halogen group, nitro group, amino group, hydroxy group, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, or 6 to 40 carbon atoms. It is an aryl group or a combination thereof, and the alkyl group, the alkenyl group or the aryl group may contain an ether bond, a ketone bond or an ester bond. R ⁹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof, and the alkyl group, the alkenyl group The group or the aryl group may contain an ether bond, a ketone bond or an ester bond. R ¹⁰ represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group or a hydroxy group, and R ¹¹ represents a hydrogen atom or a halogen group, a nitro group, an amino group Or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms or a heterocyclic group which may be substituted with a hydroxy group, and R ¹⁰ and R ¹¹ are a carbon atom to which they are bonded; Together, they may form a ring, and n4 and n5 are each an integer of 0 to 3.

R3 is a hydrogen atom in the formula (2), also ^can be ^{R 9} is a hydrogen atom in the formula (3).
The integer n1 and the integer n2 are 0 in the formula (2), and the integer n4 and the integer n5 can be 0 in the formula (3).
Examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl group. , Cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl Group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl -Cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl -Cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1- Dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl -N-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3 -Methyl-cyclopentyl group, 1-ethyl-cyclobut Til group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl- Cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl 2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group and 2-ethyl-3-methyl And til-cyclopropyl group.

  Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2- Methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3 -Pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2 -Propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3 -Mechi -3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1- Cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group Group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pente Group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4- Methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1- Butenyl group, 2,3-dimethyl-2-butenyl group, , 3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2 -Ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1 -Propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1 -Methyl-3-cyclopentenyl Group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group Group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3 -Methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group and the like.

Examples of the aryl group having 6 to 40 carbon atoms include phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenyl group M-biphenyl group, p-biphenyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group and 9-phenanthryl group Is mentioned.
The heterocyclic group is preferably an organic group composed of a 5- or 6-membered heterocyclic ring containing nitrogen, sulfur or oxygen, such as a pyrrole group, furan group, thiophene group, imidazole group, oxazole group, thiazole group, pyrazole group, An isoxazole group, an isothiazole group, a pyridine group, etc. are mentioned.
Examples of the polymer containing a unit structure preferable as the above formula (1) can be exemplified below.

Examples of aldehydes used for producing the polymer of the present invention include formaldehyde, paraformaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, capronaldehyde, 2-methylbutyraldehyde, hexyl aldehyde, undecane aldehyde, 7-methoxy. -3,7-dimethyloctylaldehyde, cyclohexanealdehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, glutaraldehyde, adipine aldehyde, saturated aliphatic aldehydes, acrolein, methacrole Heterocyclic aldehydes such as unsaturated aliphatic aldehydes such as rhein, furfural, pyridine aldehyde and thiophene aldehyde , Benzaldehyde, naphthaldehyde, anthracene carboxaldehyde, phenylbenzaldehyde, anisaldehyde, terephthalaldehyde, pyrene carboxaldehyde, phenanthrylaldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolylaldehyde, (N, N-dimethyl) And aromatic aldehydes such as amino) benzaldehyde and acetoxybenzaldehyde. In particular, an aromatic aldehyde can be preferably used.
In order to produce a polymer having a unit structure of formula (2), a carboxyl group- or carboxylic ester group-containing aldehyde can be used. Examples thereof include terephthalaldehyde acid, methyl terephthalaldehyde acid, phthalaldehyde acid and the like.

The ketones used in the production of the polymer of the present invention are diaryl ketones, and examples thereof include diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, ditolyl ketone, and 9-fluorenone.
The polymer used in the present invention is a novolak resin (corresponding to formulas (1) to (3)) obtained by condensing carbazole with aldehydes or ketones. In this condensation reaction, aldehydes or ketones can be used at a ratio of 0.1 to 10 equivalents with respect to 1 equivalent of the phenyl group of the carbazoles.
Examples of the acid catalyst used in the condensation reaction include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate, formic acid and oxalic acid. Carboxylic acids such as are used. The amount of the acid catalyst used is variously selected depending on the type of acids used. Usually, 0.001 to 10000 parts by mass, preferably 0.01 to 1000 parts by mass, more preferably 0.1 to 1000 parts by mass with respect to 100 parts by mass of carbazoles or the total of carbazoles and aldehydes or ketones. 100 parts by mass.

  The above condensation reaction is carried out without a solvent, but is usually carried out using a solvent. Any solvent that does not inhibit the reaction can be used. Examples thereof include cyclic ethers such as tetrahydrofuran and dioxane. In addition, if the acid catalyst used is a liquid such as formic acid, it can also serve as a solvent.

The reaction temperature during the condensation is usually 40 ° C to 200 ° C. The reaction time is variously selected depending on the reaction temperature, but is usually about 30 minutes to 50 hours.
The weight average molecular weight Mw of the polymer obtained as described above is usually 600 to 1,000,000 or 600 to 200,000.
The said polymer can mix and use another polymer within 30 mass% in all the polymers.

These polymers include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydrides, and polyacrylonitrile compounds.
Examples of the raw material monomer for the polyacrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate , Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 2-methoxybutyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8 -Ethyl-8-tricyclodecyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, and the like.

The raw material monomers for the polymethacrylic acid ester compound include ethyl methacrylate, normal propyl methacrylate, normal pentyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2-phenylethyl methacrylate, 2 -Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, methyl acrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, normal lauryl methacrylate Normal stearyl methacrylate , Methoxydiethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, tert-butyl methacrylate, isostearyl methacrylate, normal butoxyethyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 2-methyl-2- Adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 2-methoxybutyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclo Decyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic 6-lactone, and 2,2,3,3,4,4,4-heptafluoro-butyl methacrylate, and the like.
Examples of the acrylamide compound include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, and N, N-dimethylacrylamide.

Examples of the raw material monomer of the polymethacrylic acid amide compound include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-benzyl methacrylamide, N-phenyl methacrylamide, and N, N-dimethyl methacrylamide. .
Examples of the raw material monomer for the polyvinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
Examples of the raw material monomer for the polystyrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and hydroxystyrene.
Examples of the raw material monomer for the polymaleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

These polymers are produced by dissolving an addition polymerizable monomer and an optionally added chain transfer agent (10% or less based on the mass of the monomer) in an organic solvent, and then adding a polymerization initiator to perform a polymerization reaction. Thereafter, it can be produced by adding a polymerization terminator. The addition amount of the polymerization initiator is 1 to 10% with respect to the mass of the monomer, and the addition amount of the polymerization terminator is 0.01 to 0.2% by mass. Examples of the organic solvent used include propylene glycol monomethyl ether, propylene glycol monopropyl ether, ethyl lactate, cyclohexanone, methyl ethyl ketone, and dimethylformamide, chain transfer agents such as dodecane thiol and dodecyl thiol, and polymerization initiators such as azo Examples thereof include bisisobutyronitrile and azobiscyclohexanecarbonitrile, and examples of the polymerization terminator include 4-methoxyphenol. The reaction temperature is appropriately selected from 30 to 100 ° C., and the reaction time is appropriately selected from 1 to 48 hours.
The resist underlayer film forming composition of the present invention can contain a crosslinking agent component. Examples of the cross-linking agent include melamine type, substituted urea type, or polymer type thereof. Preferably, a cross-linking agent having at least two cross-linking substituents, methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, Compounds such as methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Moreover, the condensate of these compounds can also be used.

Moreover, as the crosslinking agent, a crosslinking agent having high heat resistance can be used. As the crosslinking agent having high heat resistance, a compound containing a crosslinking-forming substituent having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be preferably used.
Examples of this compound include a compound having a partial structure of the following formula (4) and a polymer or oligomer having a repeating unit of the following formula (5).
In formula (4), R ⁹ and R ¹⁰ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, n6 is an integer of 1 to 4, and n7 is 1 To (5-n6), and (n9 + n10) represents an integer of 2 to 5.
In formula (5), R ¹¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ¹² is an alkyl group having 1 to 10 carbon atoms, n11 is an integer of 1 to 4, and n12 is 0. To (4-n11), and (n11 + n12) represents an integer of 1 to 4. The oligomer and polymer can be used in the range of 2 to 100 or 2 to 50 repeating unit structures.
These alkyl groups and aryl groups can exemplify the above alkyl groups and aryl groups.

The compounds, polymers and oligomers of formula (4) and formula (5) are exemplified below.

The above compounds can be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, the compound of the formula (4-21) can be obtained as Asahi Organic Materials Co., Ltd., trade name TM-BIP-A.
The addition amount of the crosslinking agent varies depending on the coating solvent to be used, the base substrate to be used, the required solution viscosity, the required film shape, etc., but is 0.001 to 80% by mass with respect to the total solid content, preferably It is 0.01-50 mass%, More preferably, it is 0.05-40 mass%. These cross-linking agents may cause a cross-linking reaction by self-condensation, but when a cross-linkable substituent is present in the above-mentioned polymer of the present invention, it can cause a cross-linking reaction with those cross-linkable substituents.
In the present invention, as a catalyst for promoting the crosslinking reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid It is possible to mix acidic compounds such as acids or / and thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters. I can do it. A compounding quantity is 0.0001-20 mass% with respect to the total solid, Preferably it is 0.0005-10 mass%, Preferably it is 0.01-3 mass%.
In the coating type lower layer film forming composition for lithography of the present invention, a photoacid generator can be added in order to match the acidity with the photoresist coated on the upper layer in the lithography process. Preferred photoacid generators include, for example, onium salt photoacid generators such as bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, and phenyl-bis (trichloromethyl) -s. -Halogen-containing compound photoacid generators such as triazine, and sulfonic acid photoacid generators such as benzoin tosylate and N-hydroxysuccinimide trifluoromethanesulfonate. The said photo-acid generator is 0.2-10 mass% with respect to the total solid, Preferably it is 0.4-5 mass%.

In addition to the above, further light absorbers, rheology modifiers, adhesion aids, surfactants, and the like can be added to the resist underlayer film material for lithography of the present invention as necessary.
Examples of further light absorbers include commercially available light absorbers described in “Technical dye technology and market” (published by CMC) and “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry), such as C.I. I. Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; C.I. I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; C.I. I. Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; I. Disperse Violet 43; C.I. I. Disperse Blue 96; C.I. I. Fluorescent Brightening Agents 112, 135 and 163; C.I. I. Solvent Orange 2 and 45; C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; I. Pigment Green 10; C.I. I. Pigment Brown 2 etc. can be used suitably. The above light-absorbing agent is usually blended at a ratio of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the resist underlayer film material for lithography.

The rheology modifier mainly improves the fluidity of the resist underlayer film forming composition, and improves the film thickness uniformity of the resist underlayer film and the fillability of the resist underlayer film forming composition inside the hole, particularly in the baking process. It is added for the purpose of enhancing. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; 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 the total solid content of the resist underlayer film material for lithography.
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 (trimethylsilyl) 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 in a proportion of less than 5% by mass, preferably less than 2% by mass, based on the total solid content of the resist underlayer film material for lithography.

  In the resist underlayer film material for lithography 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 (Trade name, manufactured by Tochem Products Co., Ltd.), MegaFuck F171, F173, R-30 (trade name, manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M Limited) Fluorine surfactants such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (trade name, manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu) Mention may be made of the academic Kogyo Co., Ltd.), and the like. The blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film material for lithography of the present invention. These surfactants may be added alone or in combination of two or more.

In the present invention, the solvent for dissolving the polymer, the crosslinking agent component, the crosslinking catalyst and the like include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate. , Ethylene glycol ethyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol, propylene glycol monomethyl ether Propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol dimethyl ether, toluene, Xylene, styrene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxyethyl propionate, 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyacetate, 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate Ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1 -Methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyl lactone, acetone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, isopropyl ketone acetate, normal propyl acetate, isobutyl acetate, methanol Ethanol, isopropanol, tert-butanol, allyl alcohol, normal propanol, 2-methyl-2-butanol, isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pen Tanol, 2-ethylhexanol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy-2-butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, isopropyl Ether, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl Sulfoxide, can be used N- cyclohexyl-2-pyrrolidinone and the like. 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, propylene glycol monobutyl ether, ethyl lactate, butyl lactate, and cyclohexanone are preferable for improving the leveling property.
The resist used in the present invention is a photoresist or an electron beam resist.

  As the photoresist applied to the upper part of the resist underlayer film for lithography in the present invention, either negative type or positive type can be used, and a positive type photoresist composed of a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, depending on the acid. Chemically amplified photoresist comprising a binder having a group that decomposes to increase the alkali dissolution rate and a photoacid generator, a low molecular weight compound and photoacid that increases the alkali dissolution rate of the photoresist by decomposition with an alkali-soluble binder and acid Chemically amplified photoresist comprising a generator, comprising a binder having a group that decomposes with acid to increase the alkali dissolution rate, a low-molecular compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator Chemically amplified photoresist with Si atoms in the skeleton That there is a photoresist or the like, for example, Rohm & Hearts Co., Ltd., and trade name APEX-E.

  The electron beam resist applied on the upper part of the resist underlayer film for lithography in the present invention, for example, generates an acid by irradiation with a resin containing an Si-Si bond in the main chain and an aromatic ring at the terminal and an electron beam. A composition comprising an acid generator or a composition comprising a poly (p-hydroxystyrene) having a hydroxyl group substituted with an organic group containing N-carboxyamine and an acid generator that generates an acid upon irradiation with an electron beam It is done. In the latter electron beam resist composition, the acid generated from the acid generator by electron beam irradiation reacts with the N-carboxyaminoxy group of the polymer side chain, and the polymer side chain decomposes into a hydroxyl group to show alkali solubility and an alkali developer. To form a resist pattern. Acid generators that generate acid upon irradiation with electron beams are 1,1-bis [p-chlorophenyl] -2,2,2-trichloroethane and 1,1-bis [p-methoxyphenyl] -2,2,2. -Halogenated organic compounds such as trichloroethane, 1,1-bis [p-chlorophenyl] -2,2-dichloroethane, 2-chloro-6- (trichloromethyl) pyridine, triphenylsulfonium salts, diphenyliodonium salts, etc. Examples thereof include sulfonic acid esters such as onium salts, nitrobenzyl tosylate, and dinitrobenzyl tosylate.

  As a resist developer having a resist underlayer film formed using the resist underlayer film material for lithography of the present invention, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc. Inorganic amines, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and triethanolamine Alcohol aqueous solutions such as alcohol amines, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine 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.

Next, the resist pattern forming method of the present invention will be described. A spinner, a coater, etc. are suitably used on a substrate (for example, a transparent substrate such as a silicon / silicon dioxide coating, a glass substrate, an ITO substrate) used for manufacturing a precision integrated circuit device. After applying the resist underlayer film forming composition by a simple coating method, it is baked and cured to form a coating type underlayer film. Here, the film thickness of the resist underlayer film is preferably 0.01 to 3.0 μm. Moreover, as conditions for baking after application | coating, it is 0.5 to 120 minutes at 80-350 degreeC. Then, after forming a coating material of one to several layers directly on the resist underlayer film or on the coating type lower layer film as necessary, apply a resist and irradiate light or electron beam through a predetermined mask. A good resist pattern can be obtained by performing, developing, rinsing and drying. If necessary, post-irradiation heating (PEB: Post Exposure Bake) can be performed. Then, the resist underlayer film where the resist has been developed and removed by the above process is removed by dry etching, and a desired pattern can be formed on the substrate.
The exposure light in the photoresist is actinic radiation such as near ultraviolet, far ultraviolet, or extreme ultraviolet (for example, EUV, wavelength 13.5 nm), for example, 248 nm (KrF laser light), 193 nm (ArF laser light), Light having a wavelength such as 157 nm (F ₂ laser light) is used. The light irradiation can be used without particular limitation as long as it is a method capable of generating an acid from a photoacid generator, and the exposure amount is 1 to 2000 mJ / cm ² , or 10 to 1500 mJ / cm ² , or 50. According to ~ 1000 mJ / cm ² .
Moreover, the electron beam irradiation of an electron beam resist can be performed using an electron beam irradiation apparatus, for example.
In the present invention, a step of forming the resist underlayer film on the semiconductor substrate with the resist underlayer film forming composition, a step of forming a resist film thereon, a step of forming a resist pattern by light or electron beam irradiation and development, a resist pattern Thus, a semiconductor device can be manufactured through a step of etching the resist underlayer film and a step of processing the semiconductor substrate with the patterned resist underlayer film.

In the future, as the miniaturization of the resist pattern proceeds, there arises a problem of resolution and a problem that the resist pattern collapses after development, and it is desired to reduce the thickness of the resist. For this reason, it is difficult to obtain a resist pattern film thickness sufficient for substrate processing, and not only the resist pattern but also the resist underlayer film formed between the resist and the semiconductor substrate to be processed functions as a mask during substrate processing. The process to have it has become necessary. Unlike conventional high-etch-rate resist underlayer films, the resist underlayer film for lithography, which has a selection ratio of dry etching rates close to that of resist, is selected as a resist underlayer film for such processes, and a lower dry etching rate than resist. There has been a growing demand for a resist underlayer film for lithography having a higher ratio and a resist underlayer film for lithography having a lower dry etching rate selection ratio than a semiconductor substrate. Further, such a resist underlayer film can be provided with an antireflection ability, and can also have a function of a conventional antireflection film.
On the other hand, in order to obtain a fine resist pattern, a process of making the resist pattern and the resist underlayer film narrower than the pattern width at the time of developing the resist during dry etching of the resist underlayer film has begun to be used. Unlike the conventional high etch rate antireflection film, a resist underlayer film having a selectivity of a dry etching rate close to that of the resist has been required as a resist underlayer film for such a process. Further, such a resist underlayer film can be provided with an antireflection ability, and can also have a function of a conventional antireflection film.

  In the present invention, after forming the resist underlayer film of the present invention on the substrate, directly or on the resist underlayer film as needed, after forming one to several layers of coating material on the resist underlayer film, A resist can be applied. As a result, the pattern width of the resist becomes narrow, and even when the resist is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas.

  That is, a step of forming the resist underlayer film on the semiconductor substrate with the resist underlayer film forming composition, and forming a hard mask by a coating material containing a silicon component or the like or a hard mask (for example, silicon nitride oxide) on the semiconductor substrate. A step of forming a resist film thereon, a step of forming a resist pattern by light and electron beam irradiation and development, a step of etching the hard mask with a halogen-based gas using the resist pattern, and a patterned hard mask Thus, a semiconductor device can be manufactured through a step of etching the resist underlayer film with an oxygen-based gas or a hydrogen-based gas and a step of processing a semiconductor substrate with a halogen-based gas with the patterned resist underlayer film.

  When considering the effect as an antireflection film, the resist underlayer film forming composition for lithography of the present invention has a light absorption site incorporated into the skeleton, so there is no diffused material in the photoresist during heating and drying. Moreover, since the light absorption site has a sufficiently large light absorption performance, the effect of preventing reflected light is high.

  The composition for forming a resist underlayer film for lithography of the present invention has high thermal stability, can prevent contamination of the upper layer film by decomposition products during baking, and can provide a margin for the temperature margin of the baking process. is there.

  Furthermore, the resist underlayer film material for lithography according to the present invention has a function of preventing reflection of light depending on process conditions, and further prevents the interaction between the substrate and the photoresist, or a material or photoresist used for the photoresist. The film can be used as a film having a function of preventing an adverse effect on a substrate of a substance generated during exposure.

Synthesis example 1
In a 100 mL flask, carbazole (10.00 g, manufactured by Tokyo Chemical Industry Co., Ltd.), terephthalaldehyde acid (8.98 g, manufactured by Tokyo Chemical Industry Co., Ltd.), paratoluenesulfonic acid monohydrate (1.19 g, Kanto Chemical) (Manufactured by Co., Ltd.) was added, and 1,4-dioxane (47.07 g, manufactured by Kanto Chemical Co., Inc.) was added and stirred, and the temperature was raised to 110 ° C. and dissolved to initiate polymerization. After 24 hours, the mixture was allowed to cool and reprecipitated into water / methanol = 19/1 (1000 ml, manufactured by Kanto Chemical Co., Inc.). The obtained precipitate was filtered and dried at 80 ° C. for 12 hours with a vacuum drier to obtain the target polymer (formula (1-1), 18.0 g.
The weight average molecular weight Mw measured in terms of polystyrene by GPC was 2,900, and the polydispersity Mw / Mn was 2.13.

Synthesis example 2
In a 100 mL flask, carbazole (9.00 g, manufactured by Tokyo Chemical Industry Co., Ltd.), phthalaldehyde acid (8.08 g, manufactured by Tokyo Chemical Industry Co., Ltd.), paratoluenesulfonic acid monohydrate (1.07 g, Kanto Chemical) Co., Ltd.) was added, and toluene (42.52 g, manufactured by Kanto Chemical Co., Inc.) was added and stirred, and the temperature was raised to 110 ° C. and dissolved to initiate polymerization. After cooling to 60 ° C. after 29 hours, tetrahydroxyfuran (25.98 g, manufactured by Kanto Chemical Co., Inc.) was added and diluted, and then reprecipitated into methanol (600 ml, manufactured by Kanto Chemical Co., Ltd.). The obtained precipitate was filtered and dried with a vacuum dryer at 80 ° C. for 12 hours to obtain a target polymer (formula (1-2), 5.32 g.
The weight average molecular weight Mw measured in terms of polystyrene by GPC was 7,500, and the polydispersity Mw / Mn was 2.99.

Synthesis example 3
In a 100 mL flask, carbazole (9.00 g, manufactured by Tokyo Chemical Industry Co., Ltd.), methyl terephthalaldehyde (8.85 g, manufactured by Tokyo Chemical Industry Co., Ltd.), paratoluenesulfonic acid monohydrate (1.06 g, Kanto) Chemical Co., Ltd.) was added, and 1,4-dioxane (44.13 g, manufactured by Kanto Chemical Co., Inc.) was added and stirred, and the temperature was raised to 110 ° C. and dissolved to initiate polymerization. After 16 hours, the mixture was allowed to cool to 60 ° C. and then reprecipitated into methanol (600 ml, manufactured by Kanto Chemical Co., Inc.). The resulting precipitate was filtered and dried with a vacuum dryer at 80 ° C. for 12 hours to obtain the target polymer (formula (1-3), 6.21 g.
The weight average molecular weight Mw measured in terms of polystyrene by GPC was 2,100, and the polydispersity Mw / Mn was 1.49.

Synthesis example 4
In a 100 mL flask, carbazole (10.00 g, manufactured by Tokyo Chemical Industry Co., Ltd.), terephthalaldehyde acid (4.49 g, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrenecarboxaldehyde (6.90 g, Tokyo Chemical Industry Co., Ltd.) )), P-toluenesulfonic acid monohydrate (1.21 g, manufactured by Kanto Chemical Co., Inc.), 1,4-dioxane (52.63 g, manufactured by Kanto Chemical Co., Ltd.) was added and stirred, and 110 Polymerization was started by raising the temperature to 0 ° C and dissolving. After 32 hours, the mixture was allowed to cool to 60 ° C. and then reprecipitated into water / methanol = 1/4 (750 ml, manufactured by Kanto Chemical Co., Inc.). The obtained precipitate was filtered and dried with a vacuum dryer at 80 ° C. for 12 hours to obtain a target polymer (formula (1-4), 9.97 g).
The weight average molecular weight Mw measured in terms of polystyrene by GPC was 1,300, and the polydispersity Mw / Mn was 1.48.

Comparative Synthesis Example 1
In a 300 mL flask, carbazole (30.01 g, manufactured by Tokyo Chemical Industry Co., Ltd.), benzaldehyde (19.05 g, manufactured by Tokyo Chemical Industry Co., Ltd.), paratoluenesulfonic acid monohydrate (3.57 g, Kanto Chemical Co., Ltd.) )), And toluene (61.39 g, manufactured by Kanto Chemical Co., Inc.) and 1,4-dioxane (61.39 g, manufactured by Kanto Chemical Co., Ltd.) were added and stirred, and the mixture was heated to 110 ° C. and dissolved. Polymerization was started. After 24 hours, the mixture was allowed to cool to 60 ° C. and then reprecipitated into methanol (2000 ml, manufactured by Kanto Chemical Co., Inc.). The obtained precipitate was filtered and dried with a vacuum dryer at 80 ° C. for 12 hours to obtain the target polymer (formula (1-4), 35.98 g).
The weight average molecular weight Mw measured in terms of polystyrene by GPC was 11,200, and the polydispersity Mw / Mn was 3.58.

Example 1
To 2 g of the resin obtained in Synthesis Example 1, 0.06 g of Megafac R-30 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) is mixed as a surfactant, and 12.6 g of propylene glycol monomethyl ether acetate, propylene glycol A solution was prepared by dissolving in 5.4 g of monomethyl ether. Thereafter, the solution is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm, so that the resist underlayer film forming composition solution used in the lithography process using a multilayer film is used. Was prepared.
Example 2
To 2 g of the resin obtained in Synthesis Example 2, 0.06 g of Megafac R-30 (manufactured by Dainippon Ink Chemical Co., Ltd., trade name) is mixed as a surfactant, and 12.6 g of propylene glycol monomethyl ether acetate, cyclohexanone 5 Dissolved in 4 g to obtain a solution. Thereafter, the solution is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm, so that the resist underlayer film forming composition solution used in the lithography process using a multilayer film is used. Was prepared.
Example 3
To 2 g of the resin obtained in Synthesis Example 3, 0.06 g of Megafac R-30 (Dainippon Ink Chemical Co., Ltd., trade name) is mixed as a surfactant, and 10.8 g of propylene glycol monomethyl ether acetate, propylene glycol A solution was prepared by dissolving in 3.6 g of monomethyl ether and 3.6 g of cyclohexanone. Thereafter, the solution is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm, so that the resist underlayer film forming composition solution used in the lithography process using a multilayer film is used. Was prepared.
Example 4
To 2 g of the resin obtained in Synthesis Example 4, 0.06 g of Megafac R-30 (Dainippon Ink Chemical Co., Ltd., trade name) is mixed as a surfactant, and 10.8 g of propylene glycol monomethyl ether acetate, propylene glycol A solution was prepared by dissolving in 3.6 g of monomethyl ether and 3.6 g of cyclohexanone. Thereafter, the solution is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm, so that the resist underlayer film forming composition solution used in the lithography process using a multilayer film is used. Was prepared.

Comparative Example 1
A solution of cresol novolac resin (commercially available product, weight average molecular weight of 4000) was used.
Comparative Example 2
To the resin 2 g obtained in Comparative Synthesis Example 1, 0.06 g of Megafac R-30 (Dainippon Ink Chemical Co., Ltd., trade name) is mixed as a surfactant, and 10.8 g of propylene glycol monomethyl ether acetate, propylene A solution was prepared by dissolving in 3.6 g of glycol monomethyl ether and 3.6 g of cyclohexanone. Thereafter, the solution is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm, so that the resist underlayer film forming composition solution used in the lithography process using a multilayer film is used. Was prepared.

(Measurement of optical parameters)
The resist underlayer film solutions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied onto a silicon wafer using a spin coater. Baking was performed on a hot plate at 240 ° C. for 1 minute or at 400 ° C. for 2 minutes to form a resist underlayer film (film thickness: 0.25 μm). These resist underlayer films were measured for refractive index (n value) and optical absorption coefficient (also referred to as k value and attenuation coefficient) at a wavelength of 248 nm and a wavelength of 193 nm using a spectroscopic ellipsometer. The results are shown in Table 1.

[Table 1]
Table 1 Refractive index n and optical extinction coefficient k
――――――――――――――――――――――――――――――――――――
n k
(193 nm) (193 nm)
Example 1 240 ° C. Firing Film 1.42 0.51
Example 1 Fired film at 400 ° C. 1.43 0.49
Example 2 240 degreeC baking film 1.37 0.51
Example 2 Fired film at 400 ° C. 1.40 0.49
Example 3 240 degreeC baking film 1.42 0.52
Example 3 Fired film at 400 ° C. 1.43 0.50
Example 4 240 ° C. fired film 1.44 0.53
Example 4 Fired film at 400 ° C. 1.44 0.52
Comparative Example 1 240 ° C. fired film 1.53 0.42
Comparative Example 1 400 ° C. Baked Film Unmeasurable Not Measurable Comparative Example 2 240 ° C. Baked Film 1.56 0.68
Comparative Example 2 400 ° C. Firing Film 1.49 0.53
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(Elution test for photoresist solvent)
The resist underlayer film forming composition solutions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied onto a silicon wafer using a spin coater. The resist underlayer film (film thickness 0.20 μm) was formed by baking at 400 ° C. for 2 minutes on a hot plate. This resist underlayer film was immersed in a solvent used for the resist, for example, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone, and it was confirmed that the resist underlayer film was insoluble in the solvent.
(Measurement of dry etching rate)
The following etchers and etching gases were used to measure the dry etching rate.
ES401 (manufactured by Nippon Scientific): CF ₄
The resist underlayer film forming composition solutions prepared in Examples 1 to 4 and Comparative Example 2 were each applied onto a silicon wafer using a spin coater. Baking was performed on a hot plate at 240 ° C. for 1 minute or at 400 ° C. for 2 minutes to form a resist underlayer film (film thickness: 0.25 μm). The dry etching rate was measured using CF ₄ gas as the etching gas.
Further, the solution of Comparative Example 1 was baked on a silicon wafer at 240 ° C. for 1 minute using a spin coater to form a resist underlayer film (film thickness 0.20 μm). The dry etching rate was measured using CF ₄ gas as the etching gas, and the dry etching rates of the resist underlayer films of Examples 1 to 4 and Comparative Example 2 were compared. The results are shown in Table 2. The speed ratio is (Dry etching rate of the film obtained by baking each resist underlayer film of Examples 1 to 4 and Comparative Example 2 at each temperature) / (Dry etching of the film obtained by baking the resist underlayer film of Comparative Example 1 at 240 ° C. Speed) dry etching rate ratio.

[Table 2]
Table 2 Dry etching rate ratio ―――――――――――――――――――――――――――――――――――――
Speed ratio of 240 ° C. fired film Speed ratio of 400 ° C. fired film Example 1 0.83 0.85
Example 2 0.84 0.94
Example 3 0.84 0.90
Example 4 0.80 0.82
Comparative Example 2 0.73 0.81
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(Measurement of pattern bending resistance)
The solutions of the resist underlayer film forming compositions prepared in Examples 1 to 4 and Comparative Example 2 were each applied onto a silicon wafer with a silicon oxide film using a spin coater. A resist underlayer film (film thickness: 200 nm) was formed by baking at 400 ° C. for 2 minutes on a hot plate. A silicon hard mask forming composition solution was applied on the resist underlayer film and baked at 240 ° C. for 1 minute to form a silicon hard mask layer (film thickness 45 nm). A resist solution was applied thereon and baked at 100 ° C. for 1 minute to form a resist layer (film thickness 120 nm). Exposure was performed using a mask at a wavelength of 193 nm, post-exposure heating PEB (at 105 ° C. for 1 minute), and development was performed to obtain a resist pattern. Thereafter, dry etching was performed with a fluorine-based gas (component CF4), and the resist pattern was transferred to a hard mask. Thereafter, dry etching was performed with an oxygen-based gas (component: O2 / CO2), and the resist pattern was transferred to the resist underlayer film. Thereafter, dry etching was performed with a fluorine-based gas (component is C4F8 / O2 / Ar), and the silicon oxide film on the silicon wafer was removed. Each pattern shape at that time was observed with an electron microscope.

  As the pattern width narrows, irregular pattern bending called wiggling is likely to occur. However, the above-described steps are performed using the resist underlayer film forming composition of the above-described embodiment, and pattern wiggling occurs. The starting pattern width was observed with an electron microscope.

  Since the processing of the substrate based on the faithful pattern becomes impossible due to the occurrence of pattern bending, it is necessary to process the substrate with the pattern width (limit pattern width) immediately before the occurrence of the pattern bending. The narrower the limit pattern width at which pattern bending starts to occur, the finer the substrate can be processed. A length-measuring scanning electron microscope (manufactured by Hitachi, Ltd.) was used for measuring the resolution. The measurement results are shown in Table 3.

[Table 3]
Table 3 Limit pattern width at which pattern bending starts to occur ――――――――――――――――――――――――――――――――――― -
(When the resist underlayer film forming composition of Example 1 is used) 39.1 nm
(When the resist underlayer film forming composition of Example 2 is used) 38.2 nm
(When the resist underlayer film forming composition of Example 3 is used) 38.3 nm
(When using the resist underlayer film forming composition of Example 4) 43.1 nm
(When the resist underlayer film forming composition of Comparative Example 2 is used) 44.2 nm
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The resist underlayer film material used in the lithography process using the multilayer film of the present invention is different from the conventional high etch rate antireflection film, and the selectivity of the dry etching rate close to the photoresist or smaller than the photoresist, the semiconductor substrate Thus, it is possible to provide a resist underlayer film that has a lower dry etching rate selection ratio than the above and can also have an effect as an antireflection film. Further, it was found that the lower layer film material of the present invention has heat resistance capable of forming a hard mask on the upper layer by vapor deposition.

Claims (12)

Unit structure of the following formula (1):

(In Formula (1), A represents a structure having carbazole, B represents a structure having an aromatic ring, C represents a structure having a hydrogen atom, an alkyl group or an aromatic ring, and B and C constitute a ring together. A resist containing a polymer having a unit structure represented by 1 to 4 carboxyl groups or salts thereof, or a carboxylic acid ester group in a structure in which A, B, and C are combined. Underlayer film forming composition. The unit structure of the above formula (1) is the following formula (2):

(In the formula (2), R ¹ and R ² are each a halogen group, a nitro group, an amino group, a carboxylic acid group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon number. 6 to 40 aryl groups, or a combination thereof, and the alkyl group, the alkenyl group, and the aryl group may include an ether bond, a ketone bond, or an ester bond, and R ³ is a hydrogen atom, An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof, and the alkyl group, the alkenyl group, and the aryl group are ether bonds, It may contain a ketone bond or an ester bond, R ⁴ may be substituted with a halogen group, a nitro group, an amino group or a hydroxy group and has 6 to 6 carbon atoms Represents an aryl group or a heterocyclic group of up to 40, and R ⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group, carbon Represents an aryl group or heterocyclic group of formula 6 to 40, and R ⁴ and R ⁵ may form a ring together with the carbon atom to which they are bonded, R ⁶ is a hydrogen atom, NR ⁰ ₄ Group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof, and the alkyl group, the alkenyl group, and the aryl group are It may contain an ether bond, a ketone bond, or an ester bond, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n1 and n2 each represent an integer of 0 to 3, and n3 represents 1 to Four It is an integer.) The resist underlayer film forming composition according to claim 1. The polymer has a unit structure of the above formula (2) and a unit structure of the formula (3):

(In the formula (3), R ⁷ and R ⁸ are each a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 6 to 40 carbon atoms. And the alkyl group, the alkenyl group, or the aryl group may include an ether bond, a ketone bond, or an ester bond, and R ⁹ represents a hydrogen atom or a carbon atom number. An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof, and the alkyl group, the alkenyl group, or the aryl group is an ether bond may also contain a ketone linkage or ester bond .R ¹⁰ is halogen, it may be substituted with a nitro group, an amino group or hydroxy group An aryl group or a heterocyclic group having 6 to 40, R ¹¹ is a hydrogen atom, or a halogen group, a nitro group, an amino group, or optionally substituted by a hydroxy group an alkyl group having 1 to 10 carbon atoms, carbon Represents an aryl group or heterocyclic group of formula 6 to 40, and R ¹⁰ and R ¹¹ may form a ring together with the carbon atom to which they are bonded, and n 4 and n 5 are each 0 to 3 2. The resist underlayer film forming composition according to claim 1, which is a polymer including a polymer containing a unit structure represented by the formula (1): a molar ratio of 1 to 99:99 to 1. The resist underlayer film forming composition according to claim 2, wherein R ^{3 in} the formula (2) and R ^{9 in} the formula (3) are hydrogen atoms. The resist underlayer film forming composition according to any one of claims 2 to 3, wherein the integer n1, the integer n2 in the formula (2), the integer n4 in the formula (3), and the integer n5 are 0. Furthermore, the resist underlayer film forming composition of any one of Claim 1 thru | or 5 containing a crosslinking agent. The resist underlayer film forming composition according to any one of claims 1 to 6, further comprising an acid and / or an acid generator. The manufacturing method of the resist underlayer film obtained by apply | coating and baking the resist underlayer film forming composition of any one of Claim 1 thru | or 7 on a semiconductor substrate. A resist pattern forming method used for manufacturing a semiconductor, comprising: applying a resist underlayer film forming composition according to any one of claims 1 to 7 on a semiconductor substrate and baking the composition to form an underlayer film. . A step of forming an underlayer film on the semiconductor substrate with the resist underlayer film forming composition according to any one of claims 1 to 7, a step of forming a resist film thereon, irradiation with light or an electron beam, A method for manufacturing a semiconductor device, comprising: a step of forming a resist pattern by development; a step of etching the lower layer film with a resist pattern; and a step of processing a semiconductor substrate with a patterned lower layer film. A step of forming an underlayer film on the semiconductor substrate with the resist underlayer film forming composition according to any one of claims 1 to 7, a step of forming a hard mask thereon, and further forming a resist film thereon A step of forming a resist pattern by irradiation and development of light or electron beam, a step of etching a hard mask with the resist pattern, a step of etching the lower layer film with a patterned hard mask, and a patterned lower layer A method for manufacturing a semiconductor device, comprising a step of processing a semiconductor substrate with a film. The manufacturing method according to claim 11, wherein the hard mask is formed by vapor deposition of an inorganic substance.