Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor

Definitions

• the present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a method for forming a pattern.
• microfabrication has been carried out by lithography using a photoresist composition.
• the above-mentioned microfabrication is performed by forming a thin film of a photoresist composition on a silicon wafer, irradiating active energy rays such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, and developing the film.
• This is a processing method in which a silicon wafer is etched using a resist pattern as a protective film.
• BARC bottom anti-reflective coating
• the applicant has developed a method for lithography that has a high anti-reflection effect, no intermixing with the resist layer, provides an excellent resist pattern and wide focus depth margin, and has a high dry etching rate compared to resist.
• An antireflection film-forming composition from which an antireflection film can be obtained has been proposed (see Patent Document 1).
• the present inventors used the composition described in International Publication No. 2003/017002 pamphlet as a composition for forming a resist underlayer film, and discovered that when etching a resist underlayer film obtained from the composition for forming a resist underlayer film, It has been found that, in some cases, fine granular etching residues are generated. Generation of etching residue may reduce the yield of semiconductor devices.
• An object of the present invention is to provide a composition for forming a resist underlayer film, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a method for forming a pattern, which can suppress the generation of microscopic etching residues. .
• the present inventors conducted intensive studies and found that the above-mentioned problems could be solved, and completed the present invention having the following gist. That is, the present invention includes the following.
• [1] Contains a polymer having a repeating unit (1) represented by the following formula (1) and a repeating unit (2) other than the repeating unit (1), and a solvent, The average particle size of the polymer in the polymer solution containing the polymer is 50 nm or less, A composition for forming a resist underlayer film.
• R 1 represents a hydrogen atom, a methyl group, or a halogen atom
• R 2 represents a trivalent hydrocarbon group having 3 to 6 carbon atoms.
• the structure is a 5-membered ring or a 6-membered ring.
• the repeating unit (2) includes a repeating unit (2A) represented by the following formula (2A).
• R 11 represents a hydrogen atom, a methyl group, or a halogen atom
• Q 1 represents a single bond or a divalent linking group
• R 12 represents a hydrogen atom or a monovalent (Represents an organic group.)
• the repeating unit (2) includes a repeating unit (2A-1) represented by the following formula (2A-1) and a repeating unit (2A-2) represented by the following formula (2A-2).
• X 21 represents -O- or -N(-R)- (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). , represents a hydrogen atom, a methyl group, or a halogen atom, and R 22 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
• X 31 represents -O- or -N(-R)- (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
• R 31 represents a hydrogen atom, a methyl group, or a halogen atom
• R 32 represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocyclic aromatic group, or a substituted or unsubstituted heterocyclic aromatic group. Represents a family group.
• a semiconductor substrate; The resist underlayer film according to [8], A substrate for semiconductor processing comprising: [10] Forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [7]; forming a resist film on the resist underlayer film;
• a method for manufacturing a semiconductor device including: [11] Forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [7]; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, and then developing the resist film to obtain a resist pattern; etching the resist lower layer film using the resist pattern as a mask;
• a pattern forming method including:
• the present invention it is possible to provide a composition for forming a resist underlayer film, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a method for forming a pattern, which can suppress the generation of microscopic etching residues. .
• FIG. 1A shows the particle size distribution of sample 1st of the polymer solution of Synthesis Example 1.
• FIG. 1B shows the particle size distribution of Sample 2 of the polymer solution of Synthesis Example 1.
• FIG. 1C shows the particle size distribution of sample 3rd of the polymer solution of Synthesis Example 1.
• FIG. 2A shows the particle size distribution of sample 1st of the polymer solution of Synthesis Example 2.
• FIG. 2B shows the particle size distribution of sample 2nd of the polymer solution of Synthesis Example 2.
• FIG. 2C shows the particle size distribution of sample 3rd of the polymer solution of Synthesis Example 2.
• composition for forming resist underlayer film contains a polymer and a solvent.
• the composition for forming a resist underlayer film may contain other components.
• the average particle size of the polymer in the polymer solution containing the polymer is 50 nm or less.
• the present inventors used the composition described in International Publication No. 2003/017002 pamphlet as a composition for forming a resist underlayer film, and discovered that when etching a resist underlayer film obtained from the composition for forming a resist underlayer film, It has been found that, in some cases, fine granular etching residues are generated. Generation of etching residue may reduce the yield of semiconductor devices. Examples of causes of etching residue include metal impurities in the composition. However, as a result of studies conducted by the present inventors, it was determined that the fine granular etching residues were not caused by metal impurities.
• the polymer contained in the composition for forming a resist underlayer film affects the etching residue in the form of minute particles. It was found that there are parts of the polymer that are difficult to be etched, which causes etching residue.
• the present inventors focused on a monomer having a lactone structure and a polymerizable unsaturated bond (hereinafter sometimes referred to as a "lactone structure-containing monomer") that constitutes a polymer.
• the present inventors found that by using a polymer with a small average particle size in the polymer solution as the polymer contained in the composition for forming a resist underlayer film, microscopic etching residues can be suppressed.
• the present invention has been completed based on this discovery.
• the average particle size of the polymer in the polymer solution containing the polymer is 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less, and particularly preferably 20 nm or less.
• the lower limit of the average particle diameter of the polymer is not particularly limited, but may be 1 nm or more, 2 nm or more, or 5 nm or more.
• the average particle size of the polymer in the polymer solution can be determined by dynamic light scattering measurement. Dynamic light scattering measurement is performed using, for example, a dynamic light scattering photometer DLS-8000Ar (manufactured by Otsuka Electronics).
• the average particle size and polydispersity index can be determined from the obtained autocorrelation function by cumulant method analysis using an analysis program attached to the measuring device. Particle size distribution analysis can be performed using the Contin method.
• the polydispersity index of the present invention is, for example, 0.25 or less, 0.24 or less, 0.23 or less, 0.22 or less, 0.21 or less, and 0.20 or less. , which is 0.18 or less, and 0.15 or less.
• the number of fine granular etching residues (Cone defect number) exhibited by the composition of the present invention is, for example, 2500 or less, 2300 or less, 2000 or less, and 1500 or less, according to the Etching defect evaluation method shown in Examples. 1000 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, 300 or less, 200 or less, 100 or less, 80 70 or less, 50 or less, 30 or less, 20 or less, and 10 or less.
• the solvent in the polymer solution is preferably the solvent used for polymerization of the polymer. Therefore, it is preferable to use a polymer solution obtained by polymerizing monomers in a solvent as it is as a polymer solution for measuring the average particle size.
• the solvent used for polymerization include polyhydric alcohol derivatives. Examples of polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
• the concentration of the polymer in the polymer solution is preferably 10 to 30% by mass. If the polymer solution has such a concentration, the polymer chains will be entangled to some extent in the polymer solution, and results that are correlated with the generation of microscopic etching residues will be more likely to be obtained.
• the amount of polymer in a composition for forming a resist underlayer film is small, so even when trying to measure the average particle size of the polymer using a composition for forming a resist underlayer film, it was found that it was correlated with the generation of microscopic etching residues. Results are difficult to obtain.
• the composition for forming a resist underlayer film as a product may also contain components other than the polymer (for example, a crosslinking agent, a curing catalyst, and other components), and the composition for forming a resist underlayer film as a product may contain components other than the polymer.
• the particle size distribution obtained includes a mixture of the particle size distribution of the polymer and the particle size distribution of components other than the polymer, making it difficult to obtain results that correlate with the generation of microscopic etching residues.
• the polymer has a repeating unit (1) represented by the following formula (1).
• the polymer also has a repeating unit (2) other than the repeating unit (1).
• the polymer can be said to be a copolymer.
• R 1 represents a hydrogen atom, a methyl group, or a halogen atom
• R 2 represents a trivalent hydrocarbon group having 3 to 6 carbon atoms.
• lactone containing R 2 The structure is a 5-membered ring or a 6-membered ring.
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the repeating unit (1) represented by formula (1) include repeating units represented by the following formulas (1-1) to (1-3). (In formulas (1-1) to (1-3), R 1 represents a hydrogen atom, a methyl group, or a halogen atom.)
• R 1 in formula (1) and formulas (1-1) to (1-3) is preferably a methyl group.
• the repeating unit (2) is not particularly limited as long as it is a repeating unit other than the repeating unit (1) represented by formula (1), but includes the repeating unit (2A) represented by the following formula (2A). It is preferable.
• R 11 represents a hydrogen atom, a methyl group, or a halogen atom
• Q 1 represents a single bond or a divalent linking group
• R 12 represents a hydrogen atom or a monovalent (Represents an organic group.)
• the monovalent organic group for R 12 is not particularly limited, but includes, for example, a monovalent organic group having 1 to 30 carbon atoms.
• Examples of the monovalent organic group for R 12 include a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocyclic aromatic group, and a substituted or unsubstituted carbocyclic aromatic group.
• Examples include unsubstituted heterocyclic aromatic groups. Examples of these substituents include halogen atoms, hydroxy groups, carboxy groups, alkoxy groups, cyano groups, nitro groups, and amino groups.
• alkoxy group examples include alkoxy groups having 1 to 6 carbon atoms. Note that "1 to 10 carbon atoms" in "substituted or unsubstituted alkyl group having 1 to 10 carbon atoms" does not include the number of carbon atoms in the substituent.
• alkyl group in the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group.
• Examples of the aralkyl group in the substituted or unsubstituted aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, an anthrylmethyl group, and the like.
• Examples of the substituted or unsubstituted carbocyclic aromatic group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
• the number of carbon atoms in the substituted or unsubstituted carbocyclic aromatic group is, for example, 6 to 30.
• Examples of the substituted or unsubstituted carbocyclic aromatic group include phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, -Chlorphenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl group, p-cyanophenyl group, ⁇ -naphthyl group, ⁇ -naphthyl group , o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group
• heterocyclic aromatic group in the substituted or unsubstituted heterocyclic aromatic group examples include a pyridyl group, a quinolinyl group, and a quinoxalinyl group.
• the repeating unit (2) preferably includes a repeating unit (2A-1) represented by the following formula (2A-1) and a repeating unit (2A-2) represented by the following formula (2A-2).
• X 21 represents -O- or -N(-R)- (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
• R 22 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
• X 31 represents -O- or -N(-R)- (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
• R 31 represents a hydrogen atom, a methyl group, or a halogen atom
• R 32 represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocyclic aromatic group, or a substituted or unsubstituted heterocyclic aromatic group. Represents a family group.
• substituted or unsubstituted alkyl group having 1 to 10 carbon atoms in R 22 include, for example, specific examples of the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms in the description of R 12.
• Specific examples of the substituted or unsubstituted aralkyl group, substituted or unsubstituted carbocyclic aromatic group, and substituted or unsubstituted heterocyclic aromatic group in R 32 include the substituted or unsubstituted aromatic group in the description of R 12 .
• Specific examples include an unsubstituted aralkyl group, a substituted or unsubstituted carbocyclic aromatic group, and a substituted or unsubstituted heterocyclic aromatic group.
• R 11 in formula (2A), R 21 in formula (2A-1), and R 31 in formula (2A-2) are preferably a methyl group.
• the proportion of repeating unit (1) in the polymer is not particularly limited.
• the weight ratio of repeating unit (1) to all repeating units in the polymer is preferably 1 to 75% by weight, more preferably 5 to 60% by weight, particularly preferably 10 to 45% by weight.
• the weight ratio of repeating unit (2) to all repeating units in the polymer is not particularly limited, but is preferably 25 to 99% by weight, more preferably 40 to 95% by weight, and particularly preferably 55 to 90% by weight.
• the total weight ratio of repeating unit (2A-1) and repeating unit (2A-2) to all repeating units in the polymer is not particularly limited, but is preferably 25 to 99% by weight, more preferably 40 to 95% by weight. , 55 to 90% by weight is particularly preferred.
• the molecular weight of the polymer is not particularly limited.
• the weight average molecular weight of the polymer measured by gel permeation chromatography is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, and particularly preferably 30,000 or less.
• the lower limit of the weight average molecular weight of the polymer is not particularly limited, but the weight average molecular weight is preferably 5,000 or more.
• a polymer is obtained by radical polymerizing two or more types of monomers.
• One of the two or more monomers is a monomer represented by the following formula (1').
• the method for producing the polymer is such that the average particle size of the polymer in the polymer solution is reduced.
• Examples of such a manufacturing method include the polymer manufacturing method described in International Publication No. 2012/053434 pamphlet. Specifically, for example, polymerization methods (Z1) and (Z2) described in [0062] to [0066] of International Publication No. 2012/053434 pamphlet can be mentioned.
• the contents of WO 2012/053434 are incorporated herein to the same extent as if expressly set forth in their entirety.
• the polymer manufacturing method include the polymer manufacturing method described in Reference Example B-3 and Example B-3 of International Publication No. 2012/053434 pamphlet.
• the monomer represented by the following formula (1') in this specification is the monomer m- Corresponds to 1.
• the monomer represented by the following formula (2A'-1) in this specification is the monomer m-7 represented by the formula (m-7) in Reference Example B-3 of International Publication No. 2012/053434 pamphlet.
• the monomer represented by the following formula (2A'-2) in this specification is the monomer m-6 represented by the formula (m-6) in Reference Example B-3 of International Publication No. 2012/053434 pamphlet. corresponds to In Reference Example B-3 of International Publication No.
• the following polymerization is performed in order to design the composition of the solution Uc used in the subsequent step.
• a dropping solution containing a monomer mixture, a solvent, and a polymerization initiator was dropped into the flask from a dropping funnel at a constant dropping rate over 4 hours, and the temperature was maintained at 80° C. for 3 hours. Seven hours after the start of dropping the solution, the reaction was stopped by cooling to room temperature.
• Reference Example B-3 0.5 g of the polymerization reaction solution in the flask was sampled at 0.5, 1, 2, 3, 4, 5, 6, and 7 hours after the start of dropping the solution, and the monomer Quantification of m-1, m-6, and m-7 is being carried out.
• Example B-3 the content ratio (polymer composition) of monomer units in the polymer produced in each reaction time period is determined.
• the composition x 0 :y 0 :z 0 of Uc is determined.
• a post-step of dropping Uc was provided. ing.
• the composition ratio of monomer m-1 with a faster polymerization rate is higher than the composition ratio of monomer m-1 in the target composition.
• Example B-3 it is possible to avoid monomer m-1 being ubiquitously present in the polymer chain produced at the initial stage of polymerization at a composition ratio higher than the target composition. By doing so, entanglement of polymer chains is reduced, and as a result, a polymer having a small average particle size in the polymer solution can be obtained.
• the monomer that provides the repeating unit (1) represented by formula (1) to the polymer is a monomer represented by formula (1') below.
• R 1 and R 2 have the same meanings as R 1 and R 2 in formula (1), respectively.
• the monomer that provides the repeating unit represented by formula (1-1) to the polymer is a monomer represented by formula (1'-1) below.
• the monomer that provides the repeating unit represented by formula (1-2) to the polymer is a monomer represented by formula (1'-2) below.
• the monomer that provides the repeating unit represented by the formula (1-3) to the polymer is a monomer represented by the following formula (1'-3).
• the monomer that provides the repeating unit (2A) represented by the formula (2A) to the polymer is a monomer represented by the following formula (2A').
• the monomer that provides the repeating unit (2A-1) represented by the formula (2A-1) to the polymer is a monomer represented by the following formula (2A'-1).
• the monomer that provides the repeating unit (2A-2) represented by the formula (2A-2) to the polymer is a monomer represented by the following formula (2A'-2).
• R 11 , R 12 , and Q 1 have the same meanings as R 11 , R 12 , and Q 1 in formula (2A), respectively.
• R 21 , R 22 and X 21 have the same meanings as R 21 , R 22 and X 21 in formula (2A-1), respectively.
• R 31 , R 32 and X 31 have the same meanings as R 31 , R 32 and X 31 in formula (2A-2), respectively.
• Examples of the monomer represented by formula (2A') include acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes.
• Examples of the acrylic esters include substituted or unsubstituted alkyl acrylates in which the alkyl group has 1 to 10 carbon atoms, aralkyl esters of acrylic acid, and aryl esters of acrylic acid.
• Examples of the methacrylic acid esters include substituted or unsubstituted alkyl methacrylates in which the alkyl group has 1 to 10 carbon atoms, aralkyl esters of methacrylic acid, and aryl esters of methacrylic acid.
• Examples of acrylamides include N-alkylacrylamide, N-arylacrylamide, N,N-dialkyl acrylamide, N,N-diarylacrylamide, N-methyl-N-phenylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc. can be mentioned.
• Examples of methacrylamides include N-alkylmethacrylamide, N-arylmethacrylamide, N,N-dialkylmethacrylamide, N,N-diarylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl- Examples include N-phenyl methacrylamide.
• Examples of vinyl ethers include alkyl vinyl ethers and vinyl aryl ethers.
• vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, and the like.
• styrenes include styrene, alkylstyrene, alkoxystyrene, halogenated styrene, and carboxystyrene.
• Polymerization initiator used for polymerization, organic peroxides and diazo compounds can be used.
• Examples of the organic peroxide include diacyl peroxides, peroxydicarbonates, peroxyesters, and peroxysulfonates.
• Examples of diacyl peroxides include diacetyl peroxide, diisobutyl peroxide, didecanoyl peroxide, benzoyl peroxide, and succinic acid peroxide.
• Examples of peroxydicarbonates include diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diallyl peroxydicarbonate, and the like.
• peroxy esters examples include tert-butyl peroxyisobutyrate, tert-butyl neodecanate, and cumene peroxyneodecanate.
• peroxide sulfonates include acetylcyclohexylsulfonyl peroxide.
• diazo compounds examples include 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(4-methoxy-2,4-dimethoxy) valeronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), and the like.
• a polymerization initiator whose decomposition half-life at 80° C. is 10 hours or less.
• benzoyl peroxide and 2,2'-azobisisobutyronitrile are preferred, and 2,2'-azobisisobutyronitrile is more preferred.
• the amount of the polymerization initiator used is, for example, 0.0001 to 0.2 equivalent, preferably 0.0005 to 0.1 equivalent, based on the total amount of monomers used.
• the solvent used for polymerization is not particularly limited as long as it does not participate in the polymerization reaction and is compatible with the resulting polymer; for example, aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, etc. Examples include hydrogens, ketones, ethers, esters, amides, sulfoxides, alcohols, and polyhydric alcohol derivatives. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aliphatic hydrocarbons include n-hexane and n-octane.
• ketones include acetone, methyl ethyl ketone, and cyclohexanone.
• ethers include tetrahydrofuran and dioxane.
• esters include ethyl acetate and butyl acetate.
• amides include N,N-dimethylformamide and N,N-dimethylacetamide.
• sulfoxides include dimethyl sulfoxide.
• alcohols include methanol and ethanol.
• polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. These can be used alone or in combination of two or more.
• the polymerization temperature is not particularly limited as long as side reactions such as transfer reactions and termination reactions do not occur and the monomer is consumed and polymerization is completed, but it must be carried out in a temperature range of -100°C or higher and below the boiling point of the solvent. is preferred. Further, the concentration of the monomer in the solvent is not particularly limited, but is usually 1 to 40% by weight, preferably 10 to 30% by weight. The time for the polymerization reaction can be selected as appropriate, but is usually in the range of 2 hours to 50 hours.
• the content of the polymer in the composition for forming a resist underlayer film is not particularly limited, but is preferably 30% to 95% by mass, more preferably 50% to 90% by mass, and 60% by mass based on the film constituent components. % to 85% by weight is particularly preferred.
• the film constituent component is a component obtained by removing volatile components (solvent) from the composition for forming a resist film.
• the composition for forming a resist underlayer film preferably contains a crosslinking agent.
• the crosslinking agent included as an optional component in the composition for forming a resist underlayer film has, for example, a functional group that reacts by itself.
• crosslinking agent examples include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethylglycoluril) (POWDERLINK [registered trademark] 1174), 1, 3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis Examples include (butoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea.
• crosslinking agent is a nitrogen-containing compound having 2 to 6 substituents in one molecule represented by the following formula (1d) that bond to a nitrogen atom, as described in International Publication No. 2017/187969. Good too.
• R 1 represents a methyl group or an ethyl group. * represents a bond bonded to a nitrogen atom.
• the nitrogen-containing compound having 2 to 6 substituents represented by the formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).
• R 1 's each independently represent a methyl group or an ethyl group
• R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• glycoluril derivative represented by the formula (1E) examples include compounds represented by the following formulas (1E-1) to (1E-6).
• a nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule has 2 to 6 substituents represented by the following formula (2d) bonded to a nitrogen atom in one molecule. It can be obtained by reacting a nitrogen-containing compound with at least one compound represented by the following formula (3d).
• R 1 represents a methyl group or an ethyl group
• R 4 represents an alkyl group having 1 to 4 carbon atoms. * represents a bond bonded to a nitrogen atom.
• the glycoluril derivative represented by the formula (1E) can be obtained by reacting the glycoluril derivative represented by the following formula (2E) with at least one compound represented by the formula (3d).
• the nitrogen-containing compound having 2 to 6 substituents represented by the formula (2d) in one molecule is, for example, a glycoluril derivative represented by the following formula (2E).
• R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 each independently represents an alkyl group having 1 to 4 carbon atoms.
• glycoluril derivative represented by the formula (2E) examples include compounds represented by the following formulas (2E-1) to (2E-4). Furthermore, examples of the compound represented by the formula (3d) include compounds represented by the following formula (3d-1) and formula (3d-2).
• crosslinking agent may be a crosslinking compound represented by the following formula (G-1) or formula (G-2) described in International Publication No. 2014/208542.
• Q 1 represents a single bond or a monovalent organic group
• R 1 and R 4 each have a carbon atom number having an alkyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
• It represents an alkyl group having 2 to 10 carbon atoms
• R 2 and R 5 each represent a hydrogen atom or a methyl group
• R 3 and R 6 each represent an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. Indicates the group.
• n1 is an integer of 1 ⁇ n1 ⁇ 3, n2 is an integer of 2 ⁇ n2 ⁇ 5, n3 is an integer of 0 ⁇ n3 ⁇ 3, n4 is an integer of 0 ⁇ n4 ⁇ 3, and an integer of 3 ⁇ (n1+n2+n3+n4) ⁇ 6.
• n5 is an integer of 1 ⁇ n5 ⁇ 3, n6 is an integer of 1 ⁇ n6 ⁇ 4, n7 is an integer of 0 ⁇ n7 ⁇ 3, n8 is an integer of 0 ⁇ n8 ⁇ 3, and an integer of 2 ⁇ (n5+n6+n7+n8) ⁇ 5.
• m1 represents an integer from 2 to 10.
• the crosslinkable compound represented by the above formula (G-1) or formula (G-2) is a compound represented by the following formula (G-3) or formula (G-4), and a hydroxyl group-containing ether compound or a carbon atom. It may be obtained by reaction with several 2 to 10 alcohols.
• Q 2 represents a single bond or an m2-valent organic group.
• R 8 , R 9 , R 11 and R 12 each represent a hydrogen atom or a methyl group, and R 7 and R 10 each have 1 carbon atom. It represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.
• n9 is an integer of 1 ⁇ n9 ⁇ 3, n10 is an integer of 2 ⁇ n10 ⁇ 5, n11 is an integer of 0 ⁇ n11 ⁇ 3, n12 is an integer of 0 ⁇ n12 ⁇ 3, and an integer of 3 ⁇ (n9+n10+n11+n12) ⁇ 6. show.
• n13 is an integer of 1 ⁇ n13 ⁇ 3
• n14 is an integer of 1 ⁇ n14 ⁇ 4
• n15 is an integer of 0 ⁇ n15 ⁇ 3
• n16 is an integer of 0 ⁇ n16 ⁇ 3
• m2 represents an integer from 2 to 10.
• Me represents a methyl group.
• the content of the crosslinking agent in the composition for forming a resist underlayer film is, for example, 1% by mass to 50% by mass, preferably 5% by mass to 40% by mass, based on the polymer. It is.
• ⁇ Curing catalyst> As the curing catalyst contained as an optional component in the composition for forming a resist underlayer film, either a thermal acid generator or a photoacid generator can be used, but it is preferable to use a thermal acid generator.
• thermal acid generator examples include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridiniumphenolsulfonic acid, and pyridinium-p-hydroxybenzenesulfonic acid (pyridinium-p-toluenesulfonic acid).
• p-phenolsulfonic acid pyridinium salt pyridinium-trifluoromethanesulfonic acid
• salicylic acid camphorsulfonic acid
• 5-sulfosalicylic acid 4-chlorobenzenesulfonic acid
• 4-hydroxybenzenesulfonic acid 4-hydroxybenzenesulfonic acid
• benzenedisulfonic acid 1-naphthalenesulfonic acid
• Examples include sulfonic acid compounds and carboxylic acid compounds such as citric acid, benzoic acid, and hydroxybenzoic acid.
• Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
• onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octane sulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl) Iodonium salt compounds such as iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium Examples include sulfonium salt compounds such
• sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide. Can be mentioned.
• disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, and bis(2,4-dimethylbenzenesulfonyl). ) diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
• the content of the curing catalyst is, for example, 0.1% to 50% by weight, preferably 1% to 30% by weight, based on the crosslinking agent.
• solvent organic solvents generally used in chemical solutions for semiconductor lithography processes are preferred. Specifically, 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 monoethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, 2-hydroxyisobutyric acid Ethyl, ethyl ethoxy acetate, 2-hydroxy
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Particularly preferred are propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
• a surfactant can be further added to the composition for forming a resist underlayer film in order to prevent occurrence of pinholes, striations, etc., and to further improve coating properties against surface unevenness.
• surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol ether.
• sorbitan fatty acid esters polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
• Nonionic surfactants such as fatty acid esters, FTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, trade name) , Fluorade FC430, FC431 (manufactured by Sumitomo 3M Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., product name), etc.
• fatty acid esters such as fatty acid esters, FTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, trade name) , Fluorade FC430, FC431 (manufactured by
• surfactants organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
• the blending amount of these surfactants is not particularly limited, but is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the composition for forming a resist underlayer film.
• These surfactants may be added alone or in combination of two or more.
• the film constituent components contained in the composition for forming a resist underlayer film are, for example, 0.01% by mass to 10% by mass of the composition for forming a resist underlayer film.
• the resist underlayer film of the present invention is a cured product of the above-described composition for forming a resist underlayer film.
• the resist underlayer film can be manufactured, for example, by applying the above-described composition for forming a resist underlayer film onto a semiconductor substrate and baking the composition.
• Examples of the semiconductor substrate to which the composition for forming a resist underlayer film is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.
• the inorganic film can be formed by, for example, an ALD (atomic layer deposition) method, a CVD (chemical vapor deposition) method, a reactive sputtering method, an ion plating method, or a vacuum evaporation method. method, spin coating method (spin-on-glass: SOG).
• the inorganic film examples include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film.
• the inorganic film may be a single layer or a multilayer of two or more layers. In the case of multiple layers or more, each layer may be the same type of inorganic film or may be a different type of inorganic film.
• the thickness of the inorganic film is not particularly limited.
• the composition for forming a resist underlayer film of the present invention is applied onto such a semiconductor substrate using a suitable coating method such as a spinner or a coater. Thereafter, a resist lower layer film is formed by baking using a heating means such as a hot plate.
• the baking conditions are appropriately selected from baking temperatures of 100° C. to 400° C. and baking times of 0.3 minutes to 60 minutes.
• the baking temperature is 120°C to 350°C and the baking time is 0.5 to 30 minutes, more preferably the baking temperature is 150°C to 300°C, and the baking time is 0.8 to 10 minutes.
• the lower limit of the thickness of the resist underlayer film is, for example, 1 nm, 2 nm, 3 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 70 nm, 80 nm, 90 nm, 100 nm
• the upper limit is, for example, 10 ⁇ m, 8 ⁇ m, 5 ⁇ m. , 3 ⁇ m, 2 ⁇ m, 1 ⁇ m, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, and 200 nm.
• the method for measuring the thickness of the resist underlayer film in this specification is as follows.
• a substrate for semiconductor processing of the present invention includes a semiconductor substrate and a resist underlayer film of the present invention.
• the semiconductor substrate include the aforementioned semiconductor substrates.
• the resist underlayer film is disposed on a semiconductor substrate.
• the method for manufacturing a semiconductor device of the present invention includes at least the following steps. ⁇ A step of forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, and ⁇ A step of forming a resist film on the resist underlayer film.
• the pattern forming method of the present invention includes at least the following steps. - Forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, ⁇ Process of forming a resist film on the resist lower layer film ⁇ Process of irradiating the resist film with light or electron beam and then developing the resist film to obtain a resist pattern; ⁇ Using the resist pattern as a mask, forming the resist film Process of etching the lower layer film
• a resist film is formed on the resist underlayer film.
• the thickness of the resist film is preferably 200 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 80 nm or less. Further, the thickness of the resist film is preferably 10 nm or more, more preferably 20 nm or more, and particularly preferably 30 nm or more.
• the resist formed by coating and baking the resist underlayer film by, for example, a known method is not particularly limited as long as it responds to the light or electron beam (EB) used for irradiation.
• EB light or electron beam
• Both negative photoresists and positive photoresists can be used.
• the light or electron beam is not particularly limited, but examples include i-ray (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), EUV (extreme ultraviolet ray; 13.5 nm), and EB (electron beam). Can be mentioned. Note that in this specification, a resist that responds to EB is also referred to as a photoresist.
• photoresists there are positive type photoresists made of novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, and chemically amplified type made of a photoacid generator and a binder that has a group that decomposes with acid to increase the rate of alkali dissolution.
• Photoresist a chemically amplified photoresist consisting of a low-molecular compound, an alkali-soluble binder, and a photoacid generator that decomposes with acid to increase the alkali dissolution rate of the photoresist, and a chemically amplified photoresist that decomposes with acid to increase the alkali dissolution rate.
• photoresists consisting of a binder having a group, a low-molecular compound that is decomposed by acid to increase the alkali dissolution rate of the photoacid generator, and a photoacid generator, and resists containing metal elements.
• Examples include product name V146G manufactured by JSR Corporation, product name APEX-E manufactured by Shipley, product name PAR710 manufactured by Sumitomo Chemical Co., Ltd., and product names AR2772 and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd.
• Examples of the resist composition include the following compositions.
• Resin A having a repeating unit having an acid-decomposable group whose polar group is protected with a protecting group that is removed by the action of an acid, and an actinic ray-sensitive or Radiation sensitive resin composition.
• m represents an integer of 1 to 6.
• R 1 and R 2 each independently represent a fluorine atom or a perfluoroalkyl group.
• L 1 represents -O-, -S-, -COO-, -SO 2 -, or -SO 3 -.
• L 2 represents an alkylene group that may have a substituent or a single bond.
• W 1 represents a cyclic organic group which may have a substituent.
• M + represents a cation.
• Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
• R 1 is a hydroxy group, a sulfanyl group, or a group having 1 to 20 carbon atoms. It is a monovalent organic group.
• n is an integer of 0 to 11. When n is 2 or more, plural R 1 are the same or different.
• R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoro It is a methyl group.
• R 3 is a monovalent group having 1 to 20 carbon atoms and containing the acid dissociable group.
• Z is a single bond, an oxygen atom or a sulfur atom.
• R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 2 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom
• X 1 is a single bond
• -CO-O-* or -CO-NR 4 - * represents a bond with -Ar
• R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• Ar is one or more selected from the group consisting of a hydroxy group and a carboxyl group.
• Examples of the resist film include the following.
• R A is each independently a hydrogen atom or a methyl group.
• R 1 and R 2 are each independently a tertiary alkyl group having 4 to 6 carbon atoms.
• R 3 is each independently a fluorine atom or a methyl group.
• m is an integer of 0 to 4.
• X 1 is a single bond, a phenylene group, a naphthylene group, an ester bond, a lactone ring, It is a linking group having 1 to 12 carbon atoms and containing at least one selected from phenylene group and naphthylene group.
• X 2 is a single bond, ester bond, or amide bond.
• resist materials include the following.
• R A is a hydrogen atom or a methyl group.
• X 1 is a single bond or an ester group.
• X 2 is a linear, branched or cyclic carbon An alkylene group having 1 to 12 atoms or an arylene group having 6 to 10 carbon atoms, even if a part of the methylene group constituting the alkylene group is substituted with an ether group, ester group, or lactone ring-containing group. Often, at least one hydrogen atom contained in X 2 is substituted with a bromine atom.
• Rf 1 to Rf 4 are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, at least one of which is a fluorine atom or a trifluoromethyl group.Also, Rf 1 and Rf 2 may be combined to form a carbonyl group.
• R 1 to R 5 are each Independently, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms; , an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the
• R 1 and R 2 may be bonded together to form a ring with the sulfur atom to which they are bonded. Also good.
• R A is a hydrogen atom or a methyl group.
• R 1 is a hydrogen atom or an acid-labile group.
• R 2 is a linear, branched or cyclic carbon atom number 1 ⁇ 6 alkyl group, or a halogen atom other than bromine. ⁇ 12 alkylene group.
• X 2 is -O-, -O-CH 2 - or -NH-.
• m is an integer of 1 to 4.
• u is an integer of 0 to 3 (However, m+u is an integer from 1 to 4.)
• a resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid Contains a base material component (A) whose solubility in a developer changes due to the action of an acid and a fluorine additive component (F) which shows decomposition properties in an alkaline developer,
• the fluorine additive component (F) is a fluorine additive having a structural unit (f1) containing a base-dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).
• Rf 21 is each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group.
• n is an integer from 0 to 2. * is a bond.
• the structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).
• R is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
• X is a divalent linking group that does not have an acid-dissociable site.
• a aryl is a divalent aromatic cyclic group which may have a substituent.
• X 01 is a single bond or a divalent linking group.
• Each R 2 is independently an organic group having a fluorine atom.
• coatings examples include the following.
• Coatings comprising metal oxo-hydroxo networks with organic ligands via metal carbon bonds and/or metal carboxylate bonds.
• a coating solution comprising an organic solvent and a first organometallic compound represented by the formula RSnO (3/2-x/2) (OH) x (where 0 ⁇ x ⁇ 3), the coating solution comprising: from about 0.0025 M to about 1.5 M tin, R is an alkyl group or cycloalkyl group having 3 to 31 carbon atoms, and the alkyl group or cycloalkyl group is secondary or secondary. Coating solution, bonded to tin at the tertiary carbon atom.
• An aqueous inorganic patterning precursor solution comprising a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand comprising a peroxide group.
• Irradiation with light or electron beams is performed, for example, through a mask (reticle) for forming a predetermined pattern.
• the exposure amount and the electron beam irradiation energy are not particularly limited.
• Post Exposure Bake may be performed after irradiation with light or electron beams and before development.
• the baking temperature is not particularly limited, but is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C.
• the baking time is not particularly limited, but is preferably from 1 second to 10 minutes, more preferably from 10 seconds to 5 minutes, and particularly preferably from 30 seconds to 3 minutes.
• an alkaline developer is used for development.
• the developing temperature is, for example, 5°C to 50°C.
• the developing time is, for example, 10 seconds to 300 seconds.
• alkaline developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and secondary amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline.
• Aqueous solutions of alkalis such as quaternary ammonium salts, cyclic amines such as pyrrole and piperidine, etc. can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the aqueous solution of the alkali.
• preferred developing solutions are aqueous solutions of quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and aqueous solutions of choline.
• surfactants and the like can also be added to these developers. It is also possible to use a method in which the photoresist is developed with an organic solvent such as butyl acetate instead of the alkaline developer, and the portions of the photoresist where the alkali dissolution rate has not been improved are developed.
• the resist underlayer film is etched using the formed resist pattern as a mask.
• Etching may be dry etching or wet etching, but dry etching is preferable.
• Etching gases used for dry etching include, for example, fluorine-based gases such as CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , SF 6 ; chlorine-based gases such as Cl 2 and BCl 3 ; O 2 , O 3.
• Oxygen gas such as H 2 O; H 2 , NH 3 , CO, CO 2 , CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , C 3 H 4 , C 3 H 6 , Reducing gases such as C 3 H 8 , HF, HI, HBr, HCl, NO, NH 3 and BCl 3 ; inert gases such as He, N 2 and Ar.
• These gases may be used alone or in combination of two or more.
• Japanese Patent Laid-Open No. 11-135476 proposes a technique for etching an organic antireflection film using a mixed gas of O 2 (oxygen) gas and halogen gas.
• a semiconductor device can be manufactured by processing the semiconductor substrate by a known method (such as dry etching).
• the weight average molecular weights of the polymers shown in the synthesis examples below in this specification are the results of measurements by gel permeation chromatography (hereinafter abbreviated as GPC).
• GPC gel permeation chromatography
• Example 1 To 15.2 kg of a solution containing 3.0 kg of the polymer obtained in Synthesis Example 2, 0.729 kg of tetramethoxymethyl glycoluril (Japan Cytec Industries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174) and pyridinium-p- 0.0455 kg of toluene sulfonate was mixed. The resulting mixture was dissolved in 188.25 kg of propylene glycol monomethyl ether and 22.05 kg of propylene glycol monomethyl ether acetate to prepare a solution, thereby preparing a composition for forming a resist underlayer film.
• POWDERLINK registered trademark
• Etching defect evaluation was performed as follows. Each of the resist underlayer film forming compositions obtained in Comparative Example 1 and Example 1 was applied onto an etching defect evaluation substrate (Poly Si: 150 nm/SiO 2 : 80 nm/Si) using a spinner. It was heated on a hot plate at 205° C. for 1 minute to form a resist underlayer film (thickness: 55 nm). This film was etched using a chlorine-based mixed gas using an etching device manufactured by Lam. Thereafter, the number of defects after etching (110 nm up: per 81 cm 2 ) was confirmed using a defect inspection device (manufactured by KLA-Tencor, trade name SP1-DLS). The results are shown in Table 2.

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