Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
  • C08G10/02—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only of aldehydes
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

• the present invention relates to a resist underlayer film forming composition for forming a flattening film on a substrate having a step and a method for producing a flattened laminated substrate using the resist underlayer film.
• a thin film of a photoresist composition is formed on a substrate to be processed such as a silicon wafer, and an actinic ray such as an ultraviolet ray is radiated through a mask pattern on which a semiconductor device pattern is drawn and developed.
• a resist underlayer film forming composition containing a crosslinkable compound having an alkoxymethyl group having 2 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms is disclosed (see Patent Document 1). It is shown that the embedding property is good when it is applied to a substrate having a hole pattern.
• thermosetting resist underlayer film forming composition in order to prevent mixing when laminating a photoresist composition or a different resist underlayer film, a self-crosslinking site is introduced into the polymer resin as a main component, or a crosslinking agent.
• the coating film is thermally cured by appropriately adding a crosslinking catalyst and baking (baking) at a high temperature. Thereby, it becomes possible to stack the photoresist composition and different resist underlayer films without mixing.
• a thermosetting resist underlayer film forming composition contains a polymer having a thermal crosslinking functional group such as a hydroxy group, a crosslinking agent and an acid catalyst (acid generator), it is formed on a substrate.
• a pattern for example, hole or trench structure
• the viscosity increases due to the progress of the crosslinking reaction due to firing, and the filling property into the pattern deteriorates, and the flatness after film formation decreases. Easier to do.
• An object of the present invention is to improve the filling property in a pattern at the time of baking by enhancing the thermal reflow property of the thermosetting resist underlayer film forming composition. That is, in order to improve the thermal reflow property of the thermosetting resist underlayer film forming composition, by adding an ionic liquid to the composition, the coating film maintains a low viscosity even at high temperatures, and a crosslinking reaction during baking occurs.
• a resist underlayer film forming composition for forming a coating film having high flattening property on a substrate before the start of. And the resist underlayer film forming composition for forming a resist underlayer film which also has heat resistance is provided.
• the first aspect of the present invention relates to a resist underlayer film forming composition containing at least one ionic liquid, a polymer, a crosslinking agent, a compound that promotes a crosslinking reaction, and an organic solvent.
• a second aspect relates to the resist underlayer film forming composition according to the first aspect, wherein the ionic liquid has a crosslinking site.
• a third aspect relates to the resist underlayer film forming composition according to the first aspect, wherein the ionic liquid is contained in an amount of 1.0% by mass to 90% by mass with respect to the mass of the polymer.
• the ionic liquid has the following formula (6): [In the formula (6), R 21 represents a hydrogen atom or a methyl group, and R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a haloalkyl having 1 to 20 carbon atoms.
• Y represents an oxygen atom, a sulfur atom, a carbonyl group, or an ester group
• Z represents an alkyl group having 1 to 20 carbon atoms.
• the polymer comprises an aromatic ring of an aromatic compound (A) containing at least two amino groups and three aromatic rings of 6 to 40 carbon atoms, and a vinyl of an aromatic vinyl compound (B).
• the resist underlayer film forming composition according to the first aspect or the second aspect which comprises a novolak resin containing a structure (C) obtained by reaction with a group.
• the structure (C) has the following formula (1): [In the formula (1), R 1 is an organic group containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms, R 2 and R 3 are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group and the aryl.
• the group, the heterocyclic group is a halogen atom, a nitro group, an amino group, a formyl group, an alkoxy group, or an organic group which may be substituted with a hydroxy group, and R 2 and R 3 form a ring with each other.
• T 1 is an arylene group having 6 to 40 carbon atoms.
• T 3 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxy group, a cyano group, nitro.
• Y represents an oxygen atom, a sulfur atom, a carbonyl group, or an ester group
• Z represents an alkyl group having 1 to 10 carbon atoms.
• T 2 represents a hydrogen atom, a methyl group or a phenyl group.
• m is an integer of 0 to (5+2n), and n represents the degree of condensation of the benzene ring of the aryl group derived from T 1 .
• R 1 is represented by formula (2): [In the formula (2), Ar 1 , Ar 2 , and Ar 3 each represent a benzene ring or a naphthalene ring, and R 6 , R 7 , and R 8 are each a substituent, and are a halogen atom, a nitro group, and an amino group. And a hydroxy 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, and a combination thereof, and the alkyl group.
• the alkenyl group or the aryl group represents an organic group which may have an ether bond, a ketone bond, or an ester bond
• R 4 and R 5 are each selected from the group consisting of 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, and a combination thereof.
• the resist underlayer film forming composition according to the sixth aspect which is a divalent organic group derived from the compound represented by An eighth aspect relates to the resist underlayer film forming composition according to the sixth aspect, wherein R 1 is a divalent organic group derived from N,N′-diphenyl-1,4-phenylenediamine.
• R 3 is a hydrogen atom
• R 2 is an aryl group selected from a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group
• the aryl group is a halogen atom, a nitro group, an amino group, or a carbon atom.
• a sixth group which may be substituted with an alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxy group, or a hydroxy group.
• the present invention relates to the resist underlayer film forming composition described in the aspect.
• R 3 is a hydrogen atom
• R 2 is a phenyl group
• the phenyl group is a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
• the composition for forming a resist underlayer film according to the sixth aspect which is a group that may be substituted with an alkoxy group, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxy group, or a hydroxy group.
• An eleventh aspect relates to the resist underlayer film forming composition according to the sixth aspect, wherein T 1 is a phenylene group.
• the structure (C) has the following formula (1-1):
• R 2 and R 3 are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof.
• the alkyl group, the aryl group, and the heterocyclic group are halogen atom, nitro group, amino group, formyl group, alkoxy group, or organic group which may be substituted with a hydroxy group, and R 2 And R 3 may form a ring with each other.
• T 2 represents a hydrogen atom, a methyl group, or a phenyl group.
• the resist underlayer film forming composition according to the fifth aspect which is a unit structure of
• a thirteenth aspect relates to the resist underlayer film forming composition according to any one of the first to twelfth aspects, which further contains an acid and/or an acid generator.
• a fourteenth aspect relates to a resist underlayer film obtained by applying the resist underlayer film forming composition according to any one of the first to thirteenth aspects onto a semiconductor substrate and baking the composition.
• 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 thirteenth aspects a step of forming a resist film thereon, light or electron
• the present invention relates to a method for manufacturing a semiconductor device, which includes a step of forming a resist pattern by irradiating and developing a line, a step of etching the lower layer film with the resist pattern, and a step of processing a semiconductor substrate with the 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 the first aspect to the thirteenth aspect, a step of forming a hard mask thereon, and further thereon.
• the present invention relates to a method for manufacturing a semiconductor device, which includes a step of processing a semiconductor substrate with a patterned lower layer film.
• the composition for forming a resist underlayer film of the present invention is applied onto a substrate and filled in a pattern formed on the substrate by thermal reflow when baking, but by adding an ionic liquid, low viscosity at high temperature can be obtained. By imparting it, the thermal reflow property can be enhanced and the filling property in the pattern can be improved. Further, a silicon hard mask layer may be formed on the upper layer of the resist lower layer film by a vapor deposition method, and thus heat resistance which can withstand heat during vapor deposition is also required. The resist underlayer film is also required to have etching resistance because it processes the lower substrate according to the transferred pattern.
• the resist underlayer film of the present invention can provide a material having a well-balanced property in terms of heat resistance, flattening property, and etching resistance.
• the present invention is a resist underlayer film forming composition containing at least one ionic liquid, a polymer, a crosslinking agent, a compound that promotes a crosslinking reaction, and an organic solvent.
• the above resist underlayer film forming composition for lithography contains the above resin and a solvent. Then, it may contain a cross-linking agent and an acid, and may contain an acid generator, a surfactant, etc., if necessary.
• the solid content of this composition is 0.1% by mass to 70% by mass, or 0.1% by mass to 60% by mass.
• the solid content is the content ratio of all components excluding the solvent from the resist underlayer film forming composition. 1% by mass to 100% by mass, or 1% by mass to 99.9% by mass, or 50% by mass to 99.9% by mass, or 50% by mass to 95% by mass, or 50% by mass in the solid content. Can be contained at a rate of 90 to 90% by mass.
• the cations constituting the ionic liquid contained in the resist underlayer film forming composition of the present invention are exemplified below.
• Examples thereof include an imidazolium cation, an ammonium cation, a pyrrolidinium cation, a pyridinium cation, a piperidinium cation, a guanidinium cation, a phosphonium cation, a sulfonium cation and an oxonium cation, and an imidazolium cation is preferable.
• R 21 represents a hydrogen atom or a methyl group
• R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a haloalkyl having 1 to 20 carbon atoms.
• Y represents an oxygen atom, a sulfur atom, a carbonyl group, or an ester group
• Z represents an alkyl group having 1 to 20 carbon atoms.
• alkyl group having 1 to 20 carbon atoms examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, 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-p
• the haloalkyl group having 1 to 20 carbon atoms has 1 carbon atom in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), particularly fluorine atom.
• a halogen atom chlorine atom, bromine atom, fluorine atom, iodine atom
• alkenyl group having 2 to 10 carbon atoms examples 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
• the aryl group having 6 to 40 carbon atoms is phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group.
• Examples of the aralkyl group having 7 to 15 carbon atoms include benzyl group, phenethyl group and naphthylmethyl group.
• the alkoxy group having 1 to 20 carbon atoms is, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n.
• -Pentoxy group 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n- Propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3 -Methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group Group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-
• the alkoxy group and the alkyl group of the above alkoxyalkyl group are the same as the above, and a straight chain or branched alkyl group having 1 to 20 carbon atoms substituted with a straight chain or branched alkoxy group having 1 to 20 carbon atoms.
• Examples thereof include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group and an ethoxyethyl group.
• the heterocyclic group is preferably an organic group consisting of a 5- to 6-membered heterocyclic ring containing a nitrogen atom, a sulfur atom and an oxygen atom, and examples thereof include a pyrrole group, a furan group, a thiophene group, an imidazole group, an oxazole group and a thiazole group. Examples thereof include a pyrazole group, an isoxazole group, an isothiazole group and a pyridine group.
• Examples of the polyether group - (CH 2) n11- O- (CH 2 CH 2 O) n12- (C 1 -C 4 alkyl), or - (CH 2) n11 -O- ( CH 2 CH (CH 3 ) O) n12- (C 1 -C 4 alkyl) is included, n11 is an integer of 1 to 4, n12 is an integer of 1 to 4, and C 1 -C 4 alkyl is methyl. Examples are ethyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
• the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a carbon atom number 1 to 20 alkoxy groups, alkoxyalkyl groups, polyether groups, hydroxy groups, cyano groups, nitro groups, sulfo groups, amino groups, carbonyl groups, carboxy groups, ester groups, acetyl groups, halogen atoms and other reactive groups.
• an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxy group, an ester group, a hydroxy group and an alkoxyalkyl group are more preferable. Further, an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 10 carbon atoms are more preferable, and an allyl group is most preferable.
• imidazolium cations examples include imidazolium cations represented by the following formulas (22-1) to (22-32). Further, symmetrical imidazolium cations such as 1,3-diethylimidazolium cation; asymmetric imidazolium cations such as 1-isopropyl-3-propylimidazolium cation cation and 1-tert-butyl-3-propylimidazolium cation cation Is mentioned.
• the ammonium cation is represented by the following formula (7):
• R 11 and R 12 are the same as the definitions in the formula (6)
• R 13 is the same as the definition of R 11 and R 12 described above, but R 11 and R 12 are nitrogen. Together with the atom, it may form a 5- to 8-membered optionally substituted nitrogen-containing heterocyclic group.
• R 14 represents an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, and 1 to 1 carbon atoms.
• 20 represents an alkoxy group, an alkoxyalkyl group, a polyether group; a functional organic functional group having redox properties; or a group derived from a volatile organic solvent.
• ionic liquid of the formula (7) in which R 14 is a functional organic functional group having a redox property include the compounds of the following formulas (II) to (VIII).
• n30 represents 0 or 1.
• M represents a transition metal atom.
• R 31 , R 32 and R 33 are the same or different and represent an alkyl group, a haloalkyl group, an alkoxy group, an optionally substituted aryl group, an optionally substituted aralkyl group or an alkoxyalkyl group, and R 31 R 32 and R 32 together with the nitrogen atom may form a 5- to 8-membered nitrogen-containing cyclic group.
• R is the same or different and is a halogen atom, an alkyl group, an alkoxy group, an alkanoyl group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, a nitro group, a cyano group, an acetylamino group, a phenyl group, a benzyl group or a perfluoro group.
• Two R's, which represent or are adjacent to an alkyl group, may be taken together with the carbon atom to which they are attached to form a benzene ring.
• One of the plurality of R 1A 's represents NR 1b R 2b R 3b , and the others represent the same or different R's.
• R 1b , R 2b and R 3b are the same or different and represent an alkyl group, a haloalkyl group, an alkoxy group, an optionally substituted aryl group, an optionally substituted aralkyl group or an alkoxyalkyl group, and R 1b And R 2b may combine with a nitrogen atom to form a 5- to 8-membered nitrogen-containing cyclic group.
• One of Z 1 and Z 2 represents CH and the other represents N + -R 13 (R 13 is as defined above).
• M is a transition metal atom such as Fe, Co, Ni, Zn, Cu, Cr, V, Cd, As, Mn, Ti, Zr, Sn, Ag, In, Hg, W, Pt, Au, Ga, Ge, It shows Ru, and preferably Fe.
• the alkanoyl group is a direct group having 2 to 21 carbon atoms represented by the formula: —CO—(alkyl) (alkyl is as defined in paragraph [0019]) such as acetyl, propionyl, butyryl and the like. Mention may be made of alkanoyl groups having a chain or a branch.
• the alkoxycarbonyl group has 2 to 2 carbon atoms represented by the formula: —CO—O(alkyl) (where alkyl is as defined in paragraph [0019]) such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and the like. There are 21 straight-chain or branched alkoxycarbonyl groups.
• Examples of the perfluoroalkyl group include groups in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and examples thereof include a group represented by C q F 2q+1 (q represents an integer of 1 to 20). It is illustrated.
• R 14 is a group derived from a volatile organic solvent
• the cationic group is introduced into the organic solvent through the alkylene group, if necessary, into the organic solvent.
• the boiling point at atmospheric pressure is -1.
• the compounds which are solid or liquid at room temperature and are 00° C. to 300° C., preferably 30° C. to 300° C.
• Ethers diethyl ether, tetrahydrofuran, tetrahydropyran, diisopropyl ether, diphenyl ether, anisole, phenetole, guaiacol, etc.
• alkylene glycols ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, etc.
• Alkylene glycol monoalkyl ethers ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc.
• Alkylene glycol dialkyl ethers ethylene glycol dimethyl ether (DME), ethylene glycol dieth
• Organic Solvent represents the above organic solvent
• R a represents an alkyl group which may have a substituent.
• R represents a hydrogen atom or an alkyl group which may have a substituent.
• X represents a leaving group.
• Examples of the alkyl group which may have a substituent represented by R and R a include alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group, n-propyl group and isopropyl group.
• the alkyl group may be substituted with a group such as a fluorine atom, a methoxy group or a cyano group.
• X represents a leaving group, and specific examples thereof include a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyl group and a p-toluenesulfonyl group.
• a quaternary ammonium group into a solvent having a low boiling point and a high volatility to lead it to an ionic liquid, and the quaternary ammonium is formed by reacting a leaving group with a tertiary amine as described above.
• the amino group of the solvent containing the amino group may be quaternized.
• ammonium cation examples include ammonium cations represented by the following formulas (23-1) to (23-16).
• symmetrical ammonium cations such as tetramethylammonium cation and tetrapropylammonium cation; ethyltrimethylammonium cation, vinyltrimethylammonium cation, triethylpropylammonium cation, tributylethylammonium cation, triethylisopropylammonium cation, butyldiethylmethylammonium cation, triethyl
• the carbon number of the shortest substituent such as methoxymethylammonium cation, dimethylethylmethoxyethylammonium, dimethylethylmethoxymethylammonium, diethylmethylmethoxymethylammonium is 50% or more and less than 100% of the carbon number of the longest substituent (hereinafter Ammonium cations; trimethylpropylammonium cation, trimethylisopropylammonium cation, allyltrimethyl
• Examples of the pyrrolidinium cation include pyrrolidinium cations represented by the following formulas (24-1) to (24-7).
• Examples of the pyridinium cation include pyridinium cations represented by the following formulas (25-1) to (25-9).
• piperidinium cation examples include piperidinium cations represented by the following formulas (26-1) to (26-4).
• the guanidinium cation has the following formula (8): [In the formula (8), R 11 and R 12 are the same as the definitions in the formula (6). ] Is represented.
• the phosphonium cation has the following formula (9): [In formula (9), R 11 and R 12 have the same definitions as in formula (6), and R 13 and R 14 have the same definitions as in formula (7). However, R 11 and R 12 may form a 5- to 8-membered optionally substituted phosphorus-containing heterocyclic group together with the phosphorus atom. ] Is represented.
• Examples of the phosphonium cation include phosphonium cations represented by the following formulas (27-1) to (27-8).
• symmetrical phosphonium cations such as tetramethylphosphonium cation, tetrapropylphosphonium cation, tetraoctylphosphonium cation, and tetraphenylphosphonium cation; pseudosymmetric phosphonium cations such as trimethylethylphosphonium cation; hexyltrimethylphosphonium cation, trimethyloctylphosphonium cation, etc.
• Asymmetric phosphonium cations and the like are examples of phosphonium cations and the like.
• the sulfonium cation has the following formula (10): [In formula (10), R 11 and R 12 have the same definitions as in formula (6), and R 14 has the same definitions as in formula (7). However, R 11 and R 12 may form a 5- to 8-membered optionally substituted sulfur-containing heterocyclic group together with a sulfur atom. ] Is represented.
• sulfonium cation examples include sulfonium cations represented by the following formulas (28-1) to (28-4).
• symmetrical sulfonium cations such as trimethylsulfonium cation and tributylsulfonium cation; pseudosymmetric sulfonium cations such as diethylmethylsulfonium cation; asymmetric sulfonium cations such as dimethylpropylsulfonium and dimethylhexylsulfonium.
• the oxonium cation has the following formula (11): [In formula (11), R 11 and R 12 have the same definitions as in formula (6), and R 14 has the same definitions as in formula (7). However, R 11 and R 12 may form an optionally substituted 5- or 8-membered oxygen-containing heterocyclic group together with an oxygen atom. ] Is represented.
• the anions constituting the ionic liquid contained in the resist underlayer film forming composition of the present invention are exemplified below.
• Examples thereof include imide, halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate and methide, and more specifically (CF 3 SO 2 ) 2 N ⁇ , (CF 3 SO 2 )(FSO) 2 N ⁇ , (FSO 2 ) 2 N ⁇ , (CF 3 CF 2 SO 2 ) 2 N ⁇ , (CN) 2 N ⁇ , OH ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CF 3 CF 2 CF 2 COO ⁇ , CF 3 SO 3 ⁇ , CF 3 CF 2 SO 3 ⁇ , CF 3 CF 2 SO
• the ionic liquid contained in the resist underlayer film forming composition of the present invention comprises a combination of the above-mentioned cation and anion.
• a combination of an imidazolium cation and (CF 3 SO 2 ) 2 N ⁇ is preferable, and a combination of 1-allyl-3-methylimidazolium cation and (CF 3 SO 2 ) 2 N ⁇ is particularly preferable. ..
• the above ionic liquid is contained in an amount of 1.0% by mass to 90% by mass, preferably 5.0% by mass to 70% by mass, more preferably 5.0% by mass to 50% by mass, based on the mass of the polymer.
• ionic liquids may be used alone or in combination of two or more.
• the novolak resin has a repeating unit structure represented by the following formula (1) at the terminal.
• the polymer containing the unit structure represented by the formula (1) includes a reaction product of an organic compound containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms with an aldehyde or a ketone.
• a polymer containing a novolac resin containing a structure (C) obtained by reacting the aromatic ring of the aromatic compound (A) with the vinyl group of the aromatic vinyl compound (B) as the aromatic compound (A). is there.
• R 1 is an organic group containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms
• R 2 and R 3 are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group and the aryl.
• the group, the heterocyclic group is a halogen atom, a nitro group, an amino group, a formyl group, an alkoxy group, or an organic group which may be substituted with a hydroxy group, and R 2 and R 3 form a ring with each other.
• T 1 is an arylene group having 6 to 40 carbon atoms.
• T 3 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxy group, a cyano group, nitro.
• Y represents an oxygen atom, a sulfur atom, a carbonyl group, or an ester group
• Z represents an alkyl group having 1 to 10 carbon atoms.
• T 2 represents a hydrogen atom, a methyl group or a phenyl group.
• m is an integer of 0 to (5+2n), and n represents the degree of condensation of the benzene ring of the aryl group derived from T 1 .
• T 2 is preferably a methyl group.
• Examples of the amine contained in R 1 include a primary amine structure, a secondary amine structure, and a tertiary amine structure.
• examples of the aromatic ring include a benzene ring structure, a naphthalene ring structure, an anthracene ring structure, and a pyrene ring structure.
• R 1 is an organic group containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms, and forms the main chain of the novolak resin, and contains the above amine structure and aromatic ring structure. It can be used as a divalent organic group. Particularly, R 1 is preferably a divalent organic group containing two amino groups and three aromatic rings having 6 to 40 carbon atoms.
• R 1 can be a divalent organic group derived from a compound represented by the following formula (2).
• the aromatic ring in the formula (2) forms a novolac resin with an aldehyde or a ketone.
• a bond for forming a novolak resin is formed with an aldehyde or a ketone at any two positions of the aromatic ring in the formula (2).
• Etc. can form a bond with an aldehyde or a ketone.
• a bond can be formed between the aromatic ring and the aldehyde or ketone.
• Ar 1 , Ar 2 and Ar 3 each represent a benzene ring or a naphthalene ring
• R 6 , R 7 and R 8 each represent a substituent, and a halogen atom, a nitro group, an amino group, a hydroxy group
• the aryl group represents an organic group which may include an ether bond, a ketone bond, or an ester bond
• R 4 and R 5 are each selected from the group consisting of 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, and a combination thereof.
• n1, n2, and n3 are a number of 0 or more, and is an integer up to the maximum number with which R 6 , R 7, and R 8 can be replaced.
• n1, n2, and n3 are each an integer of 0 to 4, or 0 to 3, or 0 to 2, or 0 to 1.
• the aromatic vinyl compound (B) can be exemplified by a compound containing a vinyl group having the structure of formula (B-1).
• T 1 is an arylene group having 6 to 40 carbon atoms
• T 3 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms.
• Y represents an oxygen atom, a sulfur atom, a carbonyl group or an ester group
• Z represents an alkyl group having 1 to 10 carbon atoms.
• T 2 represents a hydrogen atom, a methyl group or a phenyl group.
• T 2 is a hydrogen atom.
• m is an integer of 0 to (5+2n), and n represents the degree of condensation of the benzene ring of the aryl group derived from T 1 .
• a specific example of the arylene group having 6 to 40 carbon atoms is a divalent group obtained by further extracting one arbitrary hydrogen atom from the aryl group described in the above paragraph [0022].
• alkyl group having 1 to 10 carbon atoms methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, 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 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, 1-
• alkenyl group having 2 to 10 carbon atoms are as described in the above paragraph [0021].
• alkoxy group having 1 to 20 carbon atoms or 1 to 10 carbon atoms are as described in the above paragraph [0024].
• heterocyclic group is as described in the above paragraph [0026].
• a heterocyclic group containing a sulfur atom is preferable for use in a high refractive index material.
• R 3 is a hydrogen atom
• R 2 is an aryl group selected from a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group
• the aryl group is a halogen atom, a nitro group, an amino group
• It may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxy group, or a hydroxy group.
• R 3 is a hydrogen atom
• R 2 is a phenyl group
• the phenyl group is a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms.
• Aldehydes used for producing the polymer of the present invention include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, capronaldehyde, 2-methylbutyraldehyde, hexylaldehyde, undecane aldehyde, 7-methoxy.
• Saturated aliphatic aldehydes such as -3,7-dimethyloctylaldehyde, cyclohexanaldehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, glutaraldehyde, adipine aldehyde, acrolein, methacrolein
• unsaturated aliphatic aldehydes furfural, pyridine aldehyde, heterocyclic aldehydes such as thiophene aldehyde, benzaldehyde, naphthaldehyde, anthracene carboxaldehyde, phenylbenzaldehyde, anisaldehyde, ethoxybenzaldehyde, n-pentyloxybenzaldehyde, n- Octyloxybenzaldehyde, trim
• the ketones used for producing 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, 9-fluorenone and the like.
• the novolak reaction of an organic compound containing at least two amino groups and at least three aryl groups having 6 to 40 carbon atoms, preferably an aromatic compound represented by the compound of formula (2), with an aldehyde or ketone is It is preferred to react the aromatic compound: aldehyde or ketone in a molar ratio of 1:0.1 to 10, 1:0.5 to 2.0, or 1:1.
• Examples of the acid catalyst used in the above condensation reaction include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, trifluoromethanesulfonic acid and the like. Organic sulfonic acids, carboxylic acids such as formic acid and oxalic acid are used.
• the amount of the acid catalyst used is variously selected according to the type of acid used. Usually, it is 0.001 part by mass to 10000 parts by mass, preferably 0.01 part by mass to 1000 parts by mass, and more preferably 0.1 part by mass to 100 parts by mass with respect to 100 parts by mass of the aromatic compound. ..
• the above condensation reaction can be performed without solvent, but is usually performed using a solvent. Any solvent can be used as long as it does not inhibit the reaction. Examples thereof include ethers such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl cellosolve, tetrahydrofuran and dioxane. Further, if the acid catalyst used is a liquid one such as formic acid, it can also serve as a solvent.
• the reaction temperature during condensation is usually 40°C to 200°C. Although the reaction time is variously selected depending on the reaction temperature, it is usually about 30 minutes to 50 hours.
• the weight average molecular weight Mw of the polymer obtained as described above is usually 500 to 1,000,000, or 600 to 200,000.
• Examples of the novolak resin obtained by the reaction of an aromatic compound and an aldehyde or ketone include novolak resins containing the following unit structures.
• R 1 in the formula (1) can be a divalent organic group derived from N,N′-diphenyl-1,4-phenylenediamine.
• This compound may have three benzene rings, and further has a benzene ring as a substituent, but similarly to the above, an aldehyde or a ketone and a bond for forming a novolak resin are formed at any two positions of these benzene rings.
• the structure (C) is added to the end of the novolak resin.
• a novolak having a unit structure represented by the following formulas (3-1) to (3-22) is a polymer having a structure represented by the formulas (C-1) to (C-22) at its terminal.
• the polymer containing the unit structure of the formula (1) is typically preferably a polymer containing the unit structure of the following formula (1-1).
• the hydroxy group in the formula (1-1) is a compound obtained by converting the alkoxy group by hydrolysis when T 3 is an alkoxy group such as a t-butoxy group in the formula (1).
• T 1 is a phenylene group and T 2 is a methyl group.
• R 2 and R 3 are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof.
• the alkyl group, the aryl group, and the heterocyclic group are halogen atom, nitro group, amino group, formyl group, alkoxy group, or an organic group which may be substituted with a hydroxy group, and R 2 and R 3 s may form a ring with each other.
• T 2 represents a hydrogen atom, a methyl group or a phenyl group.
• R 2 may be a hydrogen atom
• R 3 may be a phenyl group substituted with an alkoxy group having 1 to 10 carbon atoms.
• the novolak resin used in the present invention can have the following unit structure.
• the structure (C) existing at the end of the novolac resin can be exemplified below.
• the polymer used in the present invention has a weight average molecular weight of 600 to 1,000,000, or 600 to 200,000.
• the resist underlayer film forming composition of the present invention may contain a crosslinking agent component.
• the cross-linking agent include melamine-based, substituted urea-based or polymer-based materials thereof.
• a cross-linking agent having at least two cross-linking substituents, methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, It is a compound such as methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea or methoxymethylated thiourea.
• the condensate of these compounds can also be used.
• cross-linking agent a cross-linking agent having high heat resistance can be used.
• heat-resistant cross-linking agent a compound containing a cross-linking 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).
• the above R 15 , R 16 , R 17 and R 18 are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may be the one exemplified in paragraph [0067].
• the above compounds can be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Industry Co., Ltd.
• the compound represented by the formula (4-24) among the above-mentioned cross-linking agents can be obtained under the trade name TM-BIP-A, manufactured by Asahi Organic Materials Co., Ltd.
• the amount of the crosslinking agent added varies depending on the coating solvent used, the underlying substrate used, the required solution viscosity, the required film shape, etc., but 0.001% by mass to 80% by mass based on the total solid content, It is preferably 0.01% by mass to 50% by mass, and more preferably 0.05% by mass to 40% by mass.
• These cross-linking agents may cause a cross-linking reaction by self-condensation, but when a cross-linking substituent is present in the above-mentioned polymer of the present invention, it can cause a cross-linking reaction with the cross-linking substituent.
• ⁇ Compound that accelerates the crosslinking reaction> As the compound that accelerates the crosslinking reaction (catalyst for promoting the crosslinking reaction), p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, 5-sulfosalicylic acid, 4-phenol Acidic compounds such as sulfonic acid, pyridinium-p-phenol sulfonate, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid and/or A thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, or an organic solvent
• a photo-acid generator can be added to the resist underlayer film forming composition for lithography of the present invention 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-based photoacid generators such as triazine and sulfonic acid-based photoacid generators such as benzoin tosylate and N-hydroxysuccinimide trifluoromethanesulfonate.
• the photo-acid generator is 0.2% by mass to 10% by mass, preferably 0.4% by mass to 5% by mass, based on the total solid content.
• a light absorbing agent a rheology adjusting agent, an adhesion auxiliary agent, a surfactant, and the like can be added to the resist underlayer film material for lithography of the present invention, if necessary.
• the light absorber examples include commercially available light absorbers described in “Technology and Market of Industrial Dyes” (CMC Publishing) and “Handbook of Dyes” (edited by 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. D isperse 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; C.I. I. Pigment Green 10; C.I. I. Pigment Brown 2 and the like can be preferably used.
• the light absorbing agent is usually added in a proportion 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 particularly in the baking step, improves the film thickness uniformity of the resist underlayer film and the filling property of the resist underlayer film forming composition inside the holes. It is added for the purpose of increasing.
• phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate, dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, adipic acid derivatives such as octyl decyl adipate, and diphenyl phthalate.
• 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
• stearic acid derivatives such as normal butyl stearate and glyceryl stearate. ..
• These rheology modifiers are usually added in a proportion of less than 30% by mass based on the total solid content of the resist underlayer film material for lithography.
• Adhesion aids are added mainly for the purpose of improving the adhesion between the substrate or the resist and the resist underlayer film forming composition, and in particular, preventing the resist from peeling during development.
• Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxy.
• Alkoxysilanes such as silane, hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, silazanes such as trimethylsilylimidazole, vinyltrichlorosilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -aminopropyl Silanes such as triethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, Examples thereof include heterocyclic compounds such as mercaptoimidazole and mercaptopyrimidine, and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea.
• the resist underlayer film material for lithography of the present invention can be mixed with a surfactant in order to further improve the coating property with respect to surface unevenness without generating pinholes or installations.
• a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether.
• Polyoxyethylene alkyl allyl ethers Polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc.
• Polyoxyethylene sorbitan such as sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate
• Nonionic surfactants such as fatty acid esters, F-top (registered trademark) EF301, EF303, EF352 (above, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, R- 30, the same R-30N (above, manufactured by DIC Corporation), Florard FC430, the same FC431 (above, manufactured by 3M Japan Co., Ltd.), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, the same.
• 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.
• organic solvent for dissolving the above-mentioned polymer, crosslinking agent component, crosslinking catalyst and the like, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2 -Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl
• a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate.
• a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate.
• propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 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.
• the photoresist applied to the upper portion of the resist underlayer film for lithography in the present invention either a negative type or a positive type can be used, and a positive type photoresist composed of a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester can be used.
• a chemically amplified photoresist consisting of a binder having a group that decomposes to increase the alkali dissolution rate and a photoacid generator, a low-molecular compound and a photoacid that decompose with an alkali-soluble binder and an acid to increase the alkali dissolution rate of the photoresist
• a resin containing a Si—Si bond in the main chain and an aromatic ring at the end and an acid are generated by irradiation with an electron beam.
• a composition comprising an acid generator, or a composition comprising a poly(p-hydroxystyrene) having a hydroxy group substituted with an organic group containing N-carboxyamine and an acid generator capable of generating an acid upon irradiation with an electron beam, etc. Can be mentioned.
• the acid generated from the acid generator by electron beam irradiation reacts with the N-carboxyaminoxy group of the side chain of the polymer, the side chain of the polymer decomposes into a hydroxy group and shows alkali solubility, and alkali development occurs. It dissolves in a liquid to form a resist pattern.
• Acid generators that generate an acid upon irradiation with this electron beam 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.
• sulfonates such as onium salts, nitrobenzyl tosylate, and dinitrobenzyl tosylate.
• Examples of the developing solution for a resist having a resist underlayer film formed by using the resist underlayer film material for lithography of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.
• Inorganic alkalis 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
• alkali amines such as alcohol amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, cyclic amines such as pyrrole and piperidine, and the like can be used.
• an appropriate amount of alcohol such as isopropyl alcohol or a surfactant such as nonionic surfactant may be added to the aqueous solution of the above alkalis for use.
• preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.
• a spinner, coater or the like is appropriately formed on a substrate (eg, a silicon/silicon dioxide coating, a glass substrate, a transparent substrate such as an ITO substrate) used for manufacturing precision integrated circuit devices.
• a substrate eg, a silicon/silicon dioxide coating, a glass substrate, a transparent substrate such as an ITO substrate
• the composition is baked and cured to form a coating type underlayer film.
• the film thickness of the resist underlayer film is preferably 0.01 ⁇ m to 3.0 ⁇ m.
• the condition for baking after coating is 80 to 400° C. for 0.5 to 120 minutes.
• resist underlayer film After that, directly on the resist underlayer film, or after forming one or several layers of coating material on the coating type underlayer film as necessary, apply resist and irradiate light or electron beam through a predetermined mask.
• a good resist pattern can be obtained by performing development, rinsing and drying. If necessary, post-irradiation heating with light or an electron beam (PEB: Post Exposure Bake) can be performed. Then, the resist underlayer film in the portion where the resist is developed and removed in the above step is removed by dry etching to form a desired pattern on the substrate.
• PEB Post Exposure Bake
• the exposure light from the photoresist is actinic rays such as near-ultraviolet rays, far-ultraviolet rays, or extreme ultraviolet rays (for example, EUV, wavelength 13.5 nm), such as 248 nm (KrF laser light), 193 nm (ArF laser light), Light having a wavelength such as 157 nm (F 2 laser light) is used.
• Light irradiation can be used without particular limitation as long as it is a method capable of generating an acid from a photo-acid generator, and the exposure amount is 1 mJ/cm 2 to 2000 mJ/cm 2 , or 10 mJ/cm 2 to 1500 mJ. / cm 2, or by 50 mJ / cm 2 to 1000 mJ / cm 2.
• the electron beam irradiation of the electron beam resist can be performed using, for example, an electron beam irradiation device.
• a step of forming a resist underlayer film on a semiconductor substrate with a 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
• the semiconductor device can be manufactured through the step of etching the resist underlayer film and the step of processing the semiconductor substrate with the patterned resist underlayer film.
• resist underlayer film for lithography having a low dry etching rate selection ratio as compared with a resist underlayer film for lithography or a semiconductor substrate.
• a resist underlayer film can be provided with an antireflection function, and can also have the function of a conventional antireflection film.
• a process of making the resist pattern and the resist underlayer film thinner than the pattern width during resist development during the dry etching of the resist underlayer film is also beginning to be used.
• a resist underlayer film having a dry etching rate selection ratio close to that of a resist has been required.
• such a resist underlayer film can be provided with an antireflection function, and can also have the function of a conventional antireflection film.
• the substrate after forming the resist underlayer film of the present invention on the substrate, directly on the resist underlayer film, or after forming one to several layers of coating material on the resist underlayer film, if necessary, 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.
• a hard mask made of a coating material containing a silicon component or the like or a hard mask by vapor deposition for example, silicon nitride oxide
• Step further forming a resist film thereon, forming a resist pattern by irradiation with light or an electron beam and developing, etching the hard mask with a halogen-based gas by the resist pattern, patterned hard mask
• 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 a patterned resist underlayer film.
• the resist underlayer film forming composition for lithography of the present invention when considering the effect as an antireflection film, since the light absorption site is incorporated into the skeleton, there is no diffused substance in the photoresist during heating and drying, Further, since the light absorption portion has a sufficiently large light absorption performance, the reflected light prevention effect is high.
• the resist underlayer film forming composition for lithography of the present invention has high thermal stability, can prevent the upper layer film from being contaminated by decomposition products at the time of firing, and can provide a margin in the temperature margin of the firing step. is there.
• the resist underlayer film material for lithography of the present invention has a function of preventing reflection of light depending on process conditions, and further, prevention of interaction between a substrate and a photoresist or a material used for a photoresist or a photoresist.
• the weight average molecular weight and polydispersity shown in Synthesis Example 1 below are based on the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in the present specification).
• GPC gel permeation chromatography
• a GPC device manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions are as follows.
• Example 1 1.00 g of the polymer obtained in Synthesis Example 1 and 4,4′-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol as a cross-linking agent.
• Example 2 1.00 g of the polymer obtained in Synthesis Example 1 and 4,4′-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol as a cross-linking agent.
• Example 3 1.00 g of the polymer obtained in Synthesis Example 1 and 4,4′-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol as a cross-linking agent.
• Example 4 1.00 g of the polymer obtained in Synthesis Example 1 and 4,4′-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol as a cross-linking agent.
• Example 5 1.00 g of the polymer obtained in Synthesis Example 1 and 4,4′-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol as a cross-linking agent.
• Example 6 1.00 g of the polymer obtained in Synthesis Example 1 and 4,4′-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol as a cross-linking agent.
• Example 7 1.00 g of the polymer obtained in Synthesis Example 1 and 4,4′-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol as a cross-linking agent.
• surfactant manufactured by DIC Corporation, product name: Megafac [trade name] R-30N, fluorine-based surfactant
• ionic liquid manufactured by Tokyo Chemical Industry Co., Ltd., 1-ethyl-3-methylimidazolium trifluoromethanesulfonate 0.40 g, propylene glycol monomethyl ether 1.38 g, and propylene glycol monomethyl ether acetate 3.22 g
• the composition was dissolved to prepare a resist underlayer film forming composition.
• (Comparative Example 1) 1.00 g of the polymer obtained in Synthesis Example 1 and 4,4'-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol as a cross-linking agent. 20 g, 0.020 g of pyridinium-p-phenol sulfonate as an acid catalyst, 0.001 g of surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-30N, fluorine-based surfactant), and propylene glycol monomethyl It was dissolved in 1.31 g of ether and 3.07 g of propylene glycol monomethyl ether acetate to prepare a resist underlayer film forming composition.
• surfactant manufactured by DIC Corporation, product name: Megafac [trade name] R-30N, fluorine-based surfactant
• the resist underlayer film forming compositions prepared in Examples 1 to 7 and Comparative Example 1 were each applied on a silicon wafer using a spin coater.
• the resist underlayer film (film thickness 0.8 ⁇ m) was formed by baking on a hot plate at 240° C. for 1 minute and further at 400° C. for 1 minute.
• This resist underlayer film was immersed in propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, which are solvents used for the resist, and it was confirmed that the resist underlayer film was insoluble in those solvents.
• a SiO 2 substrate having a trench pattern with a width of 100 nm, a pitch width of 175 nm, and a depth of 800 nm was used.
• the coating film thicknesses of a dense pattern area (DENSE) in which patterns having a trench width of 100 nm and a pitch of 175 nm were densely compared with an open area (OPEN) in which a pattern 1400 ⁇ m away from the dense area was not formed were compared.
• the resist underlayer film forming compositions of Examples 1 to 7 and Comparative Example 1 were applied on the above substrate to a thickness of 800 nm, and then baked at 240° C. for 60 seconds and further at 400° C. for 60 seconds.
• the step coverage of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the film thickness between the dense area (patterned portion) and the open area (non-patterned portion) of the stepped substrate
• the flatness was evaluated by measuring the difference (which is the coating step between the dense area and the open area and is called Bias).
• Table 1 shows the values of the film thickness and the coating step in each area. In the flatness evaluation, the smaller the value of Bias, the higher the flatness. Comparing the coverage of the stepped substrate, the results of Examples 1 to 7 show that the applied step difference between the pattern area and the open area is smaller than that of Comparative Example 1. Therefore, the results of Examples 1 to 7 are shown. It can be said that the resist underlayer film obtained from the resist underlayer film forming composition has good flatness.
• a composition when a photoresist composition or a different resist underlayer film is laminated, mixing does not occur, and the thermal reflow property of the polymer is enhanced to form a resist underlayer film with improved filling property in a pattern at the time of baking.
• a composition can be provided.

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