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
  • G03F7/091—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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • 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

Definitions

• Lower layer antireflection film-forming composition comprising an aromatic sulfonate compound and a photoacid generator
• the present invention relates to a lower antireflection film forming composition used in a lithography process for manufacturing a semiconductor device, and a photoresist pattern forming method using the lower antireflection film forming composition. More specifically, the present invention relates to a lower antireflection film forming composition for forming a lower antireflection film that can be developed with an alkaline developer used for developing a photoresist. Further, the present invention relates to a method for forming a photoresist pattern by simultaneously developing a photoresist and a lower antireflection film using the lower antireflection film forming composition. Background art
• microfabrication by lithography 1 using a photoresist is performed.
• Microfabrication is obtained by forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating it with actinic rays such as ultraviolet rays through a mask pattern on which a device pattern is drawn, and developing it.
• actinic rays such as ultraviolet rays
• fine concaves and convexes corresponding to the pattern are formed on the substrate surface by etching the substrate using the photoresist pattern as a protective film.
• the ion implantation process in semiconductor device manufacturing is a process of introducing impurities into a semiconductor substrate using a photoresist pattern as a saddle, and avoids damaging the substrate surface.
• a dry etching process cannot be performed. Therefore, in forming a photoresist pattern for the ion implantation process, an antireflection film that needs to be removed by dry etching cannot be used as a lower layer of the photoresist.
• the photoresist pattern that has been used as a vertical pattern in the ion implantation process so far is the influence of standing wave caused by reflection of exposure irradiation light from the substrate whose line width is wide, and exposure irradiation due to the step of the substrate.
• Reflection problems have been solved by using dye-containing photoresists and anti-reflection coatings on the top of the photoresist because they are less susceptible to diffuse reflection of light.
• the photoresist used in the ion implantation process has begun to require a fine pattern, and it has become necessary to use an antireflection film under the photoresist. .
• Patent Document 1 US Patent No. 6156479
• Patent Document 2 Japanese Patent No. 2686898
• Patent Document 3 Japanese Patent Laid-Open No. 9-78031
• Patent Document 4 Japanese Patent Laid-Open No. 11-72925
• Patent Document 5 International Publication No. 03Z057678 Pamphlet
• Patent Document 6 International Publication No. 03Z058345 Pamphlet Disclosure of the invention
• the present invention has been made in view of the above circumstances, and is a lower antireflection film soluble in an alkaline developer used for developing a photoresist, and a composition for forming the lower antireflection film
• the purpose is to provide goods.
• an object of the present invention is to provide a composition for forming a lower antireflection film used for manufacturing a semiconductor device.
• the lower layer can be dissolved in an alkaline developer without being intermixed with the photoresist applied and formed on the upper layer, can be developed and removed simultaneously with the photoresist, and can provide a photoresist pattern with a good shape. It is to provide an antireflection film. It is another object of the present invention to provide a method for forming a photoresist pattern used for manufacturing a semiconductor device using the lower antireflection film forming composition.
• the present invention provides, as a first aspect, a composition for forming an underlayer antireflection film for forming an underlayer antireflection film that is developed together with a photoresist with an alkaline developer.
• Formula (2) :
• a and A represent a tetravalent organic group
• B represents a trivalent organic group
• B represents a divalent organic group
• a lower layer characterized in that it contains a polyamic acid having a structure represented by the following formula: a bridged compound having two or more epoxy groups, an aromatic sulfonic acid ester compound, a photoacid generator and a solvent.
• Antireflection film-forming composition a polyamic acid having a structure represented by the following formula: a bridged compound having two or more epoxy groups, an aromatic sulfonic acid ester compound, a photoacid generator and a solvent.
• composition for forming an underlayer antireflection film according to the first aspect further comprising a light-absorbing compound
• composition for forming a lower antireflection film according to the first aspect further comprising an aromatic carboxylic acid compound,
• the lower layer antireflection film-forming composition according to the first aspect wherein the crosslinkable compound is a compound having two to four epoxy groups,
• the composition for forming an antireflection film for a lower layer according to the first aspect wherein the photoacid generator is a iodine salt compound or a sulfo-chloride compound,
• the aromatic sulfonate ester compound is represented by the formula (3):
• Ar is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a nitro group, a cyan group, an amino group, a halogen group, a carboxyl group, and carbon. Substituted by a group selected from alkoxy groups having 1 to 6 atoms !, may be! /, Represents a benzene ring, a naphthalene ring or an anthracene ring, and R and R are each independently ,
• a composition for forming an underlayer antireflection film according to the first aspect which is a compound having a structure represented by:
• the lower layer reflection according to the first aspect is characterized in that the aromatic sulfonate ester compound is a compound having two to four structures represented by the formula (3).
• Prevention film forming composition As an eighth aspect, the antireflective film-forming composition according to the second aspect, wherein the light-absorbing compound is a naphthalenecarboxylic acid ester compound,
• the lower layer antireflection according to the eighth aspect characterized in that the naphthalenecarboxylic acid ester compound is a compound produced by reacting a naphthalenecarboxylic acid compound and an epoxy compound.
• a film-forming composition characterized in that the naphthalenecarboxylic acid ester compound is a compound produced by reacting a naphthalenecarboxylic acid compound and an epoxy compound.
• the lower-layer antireflection film-forming composition according to the third aspect wherein the aromatic carboxylic acid compound is an aromatic carboxylic acid compound having a phenolic hydroxyl group,
• the lower-layer antireflection film-forming composition according to the third aspect, wherein the aromatic carboxylic acid compound is a naphthalenecarboxylic acid compound having a phenolic hydroxyl group,
• the polyamic acid is represented by formulas (4) and (5):
• the polyamic acid is represented by formulas (6) and (7):
• a composition for forming a lower antireflection film according to the first aspect characterized in that it is a polyamic acid
• composition for forming an underlayer antireflection film of the present invention does not cause intermixing with the photoresist, dissolves in an alkaline developer used for developing the photoresist, and develops and removes at the same time as the photoresist.
• a possible lower antireflection film can be formed.
• the lower antireflection film formed from the lower antireflection film-forming composition of the present invention can be removed without dry etching. Therefore, it can be used in a semiconductor device manufacturing process including a process sensitive to damage to the substrate surface by dry etching, such as an ion implantation process.
• the lower layer reaction of the present invention comprising an aromatic sulfonic acid ester compound and a photoacid generator.
• the lower antireflective coating formed from the anti-reflective coating forming composition can easily adjust its acidity to the same level as the acidity of the photoresist, so that a more rectangular photoresist pattern can be formed. Can do.
• the composition for forming a lower antireflection film of the present invention comprises a polyamic acid having a structure represented by the above formula (1) and the above formula (2), a crosslinkable compound having two or more epoxy groups, an aromatic Group sulfonic acid ester compounds, photoacid generators and solvents.
• the lower layer antireflection film-forming composition of the present invention can contain a light-absorbing compound, an aromatic carboxylic acid compound, a surfactant, and the like.
• the ratio of the solid content in the lower antireflection film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved, but is, for example, 1 to 50 mass%, or 3 to 30 It is mass%, or 5 to 25 mass%, or 10 to 15 mass%.
• the solid content is a value obtained by removing the solvent component from all the components of the lower layer antireflection film-forming composition.
• composition for forming a lower antireflection film of the present invention will be specifically described.
• the underlayer antireflection film-forming composition of the present invention comprises a polyamic acid having a structure represented by the formula (1) and a structure represented by the formula (2).
• A represents a tetravalent organic group
• B represents a trivalent organic group
• 1 1 1 includes, for example, formulas (8) to (16) (wherein X is an alkyl group having 1 to 5 carbon atoms, chlorine atom, bromine atom, fluorine atom, 1 to 5 carbon atoms) Represents an alkoxy group, a hydroxyl group, a ruboxyl group, a phenoxy group, a trifluoromethyl group or a -tro group, and m is 0, 1 or
• Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a cyclopentyl group, and a normal pentyl group.
• Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, a cyclopentyloxy group, and a normal pentyloxy group.
• Examples of B include formulas (17) to (24) (wherein Y is a group having 1 to 5 carbon atoms)
• A represents a tetravalent organic group
• B represents a divalent organic group
• Examples of 2 2 2 include the above formulas (8) to (16).
• Examples of B include formulas (25) to (34) (wherein Z is a group having 1 to 5 carbon atoms)
• the weight average molecular weight of the polyamic acid used in the present invention is, for example, 1000 to 100,000, or 1500 to 50000, or 2000 to 30000, or 5000 to 10,000 in terms of polystyrene. .
• the weight average molecular weight is smaller than the above value, the solubility of the lower antireflection film to be formed in the solvent used for the photoresist is increased. As a result, the lower antireflection film is intermixed with the photoresist. If force s to cause is there.
• the lower antireflection film to be formed is insufficiently soluble in an alkaline developer used for developing the photoresist, and the residue of the lower antireflection film after development is insufficient. May exist.
• the method for obtaining the polyamic acid contained in the composition for forming an underlayer antireflection film of the present invention is not particularly limited, and can be produced by an existing method.
• a polyamic acid can be produced by reacting and polymerizing a diamine compound with a tetracarboxylic dianhydride compound such as tetra-strength rubonic acid or a derivative thereof or a dicarboxylic acid dihalogen compound.
• a polyamic acid can be produced by decomposing the silyl ester moiety with an acid.
• the polyamic acid contained in the lower antireflection film-forming composition of the present invention includes (a) a tetracarboxylic dianhydride compound, (b) a diamine compound having at least one carboxyl group, and (c) ) Can be manufactured from Giamny compound.
• the (a) tetracarboxylic dianhydride compound used in the production of the polyamic acid used in the present invention is not particularly limited.
• the tetracarboxylic dianhydride compound may be used alone or in combination of two or more.
• Specific examples include pyromellitic dianhydride, 3, 3 ', 4, 4, biphenyl tetracarboxylic dianhydride, 3, 3', 4, 4, monobenzophenone tetracarboxylic dianhydride 3, 3 ', 4, 4'-diphenyl ether tetracarboxylic dianhydride, 4, 4' (hexafluoroisopropylidene) diphthalic dianhydride and 3, 3 ', 4, 4'-diphenol -Aromatic tetra force such as sulfone tetracarboxylic dianhydride Rubonic dianhydride, 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, 1, 2 dimethyl-1, 2, 3, 4 Cyclobutane tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl- 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane te
• At least one carboxylic acid used in the production of the polyamic acid used in the present invention The diamine compound having a syl group is not particularly limited. Examples of the diamine compound having at least one carboxyl group (b) include diamine compounds having 1 to 3 carboxyl groups. (B) The diamine compound having at least one carboxyl group may be used alone or in combination of two or more.
• 2,4 diaminobenzoic acid 2,5 diaminobenzoic acid, 3,5 diaminobenzoic acid, 4,6 diamino-1,3 benzenedicarboxylic acid, 2,5 diamino-1,4 benzenedicarboxylic Acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4 amino-3-carboxyphenyl) sulfone, bis (4- Amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5, monodimethylbiphenyl, 4, 4, 1, diamino 1, 3, 3, 1 dicarboxy 1, 5, 5, 1, dimethoxy biphenyl, 1, 4 bis (4 amino-3 carboxyphenoxy) benzene, 1, 3-
• the (c) diamine compound used in the production of the polyamic acid used in the present invention is not particularly limited.
• a diamine compound may be used alone, or two or more diamine compounds may be used simultaneously. Specific examples include 2,4 diaminophenol, 3,5 diaminophenol, 2,5 diaminophenol, 4,6 diaminole: / noresinole, 2,5 diaminohydroquinone, bis (3-amino-4- Hydroxyphenol) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenol) ether, bis (3-amino-4-hydroxyphenol) ) Methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-1,3,5-dihydroxyphenol) methane, bis (3-amino-4-hydroxyphenol) sulfone Bis (4-amino-3-hydroxyphenol) sulfone, bis (4 amino-3,5 dihydroxyphenol) sul
• the ratio of (b) the diamine compound having at least one carboxyl group in the total diamine compound used is, for example, 1 to 99% by mass, or 5 -80 mass%, or 10-60 mass%, or 20-50 mass%, or 30-40 mass%.
• the ratio of the diamine compound having at least one carboxyl group is less than this, the lower antireflection film to be formed has insufficient solubility in an alkaline developer.
• the polyamic acid used in the present invention is produced from (a) a tetracarboxylic dianhydride compound, (b) a diamine compound having at least one carboxyl group, and (c) a diamine compound.
• the ratio of the total number of moles of the diamine compound used to the total number of moles of the tetracarboxylic dianhydride compound is preferably 0.8 to 1.2. As in the normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the polyamic acid produced and the higher the molecular weight.
• the reaction temperature of the diamine compound and the tetracarboxylic dianhydride compound is 20 ° C to 150 ° C, preferably 5 ° C to 100 ° C. You can choose.
• High molecular weight polyamic acid can be obtained at a reaction temperature of 5 ° C to 40 ° C and a reaction time of 1 to 48 hours.
• a reaction time of 10 hours or longer at 40 ° C. to 80 ° C. is more preferable.
• the reaction of the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent.
• Solvents that can be used include N, N dimethylformamide, N, N dimethylacetamide, N-methylpyrrolidone, N vinylpyrrolidone, N-methylcaprolacta Dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, y butyrolatatane, ethyl acetate, butyl acetate, ethyl lactic acid, methyl 3-methoxypropionate, methyl 2-methoxypropionate, 3-ethyl methoxypropionate, 2-methoxypropionate, 3 ethoxypropionate, 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glyconoresin methinoate ethere, diethylene glycono lesino en
• the solution containing the polyamic acid thus obtained can be used as it is for the preparation of the lower antireflection film-forming composition.
• the polyamic acid can be poured into a poor solvent such as methanol or ethanol, precipitated, isolated and used.
• Examples of the polyamic acid contained in the lower antireflection film-forming composition of the present invention include polyamic acids having structures represented by the above formulas (4) and (5).
• the polyamic acid having the structure represented by the formula (4) and the formula (5) includes, for example, (a) a tetracarboxylic dianhydride compound, 3,5-diaminobenzoic acid and bis (4 aminophenol). It can be obtained by reacting with sulfone.
• Examples of the polyamic acid contained in the composition for forming an underlayer antireflection film of the present invention include polyamic acids having structures represented by the above formulas (6) and (7).
• Polyamic acids having the structures represented by the above formulas (6) and (7) are, for example, 4, 4 ′ (hexafluoro (Luoroisopropylidene) diphthalic dianhydride can be obtained by reacting (b) a diamine compound having at least one carboxyl group and (C) a diamine compound.
• the polyamic acid contained in the lower antireflection film-forming composition of the present invention is basically represented by the structure represented by the formula (1) and the formula (2) except for the terminal portion. Or a structure represented by the formula (4) and a structure represented by the formula (5), or a structure represented by the formula (6) and the structure represented by the formula (6) Polyamic acid having a structure and a force represented by the formula (7) can be preferably used.
• Examples of the polyamic acid contained in the composition for forming an underlayer antireflection film of the present invention include the following polyamic acids and formulas (35) to (43) (wherein p, p, p and p are poly
• 1 2 3 4 represents the proportion of each structure in the amic acid).
• the formulas (35) to (42) are one kind of tetracarboxylic dianhydride compound and two kinds of diamine compounds, and the polyamic acid produced, and the formula (43) is two kinds of tetracarboxylic dianhydrides. It is a polyamic acid produced from a compound and two diamine compounds.
• the underlayer antireflection film-forming composition of the present invention contains a crosslinkable compound having two or more epoxy groups.
• Such a crosslinkable compound is not particularly limited as long as it is a compound having two or more epoxy groups.
• a compound having 2 to 4 epoxy groups is a compound having 2 to 4 epoxy groups.
• crosslinkable compound having two or more epoxy groups include tris (2,3 epoxypropyl) isocyanurate, 1,4 butanediol diglycidyl ether, 1,2 epoxy 4 (epoxy ethinole ) Cyclohexane, glyceron tritriglycidino rea Ter, diethylene glycol diglycidyl ether, 2, 6 diglycidyl phenyl glycidyl ether, 1, 1, 3 tris [p— (2, 3 epoxypropoxy) phenol] propane, 1, 2 cyclohexanedicarboxylic acid di Glycidyl ester, 4,4,1-methylenebis (N, N diglycidyl dilin), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether and bisphenol A Examples thereof include diglycidyl ether and pentaerythri
• a polymer having an epoxy group can be used as the compound having two or more epoxy groups.
• any polymer having an epoxy group can be used without particular limitation.
• the polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. Further, it can be produced by a reaction between a polymer compound having a hydroxyl group and a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate.
• addition polymers such as polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate, And polycondensation polymers such as epoxy novolac.
• the weight average molecular weight of such a polymer is, for example, 500-200000, or 1000-50000.
• Examples of the compound having two or more epoxy groups include YH-434, YH434L (manufactured by Toto Kasei Co., Ltd.), which are epoxy resins having an amino group, and epoxy resins having a cyclohexene oxide structure.
• Epicoat 152, 154 above, made by Japan Epoxy Resin Co., Ltd.
• EPPN201, 202 above, made by Nihon Shakuyaku Co., Ltd.
• a non-polymer compound is used as the compound having two or more epoxy groups, for example, 2 to 10, or 2 to 4, or 2 to 3, or 3 to 5 epoxy groups are used.
• a compound having is preferably used.
• the content of the crosslinkable compound having two or more epoxy groups in the lower antireflection film-forming yarn composition of the present invention is, for example, 5 to 70 parts by mass with respect to 100 parts by mass of the polyamic acid. Or 10 to 60 parts by mass, preferably 15 to 45 parts by mass, or 20 to 40 parts by mass.
• the content of the crosslinkable compound having two or more epoxy groups is smaller than the above value, the curing degree of the lower antireflection film is insufficient, which may dissolve in the photoresist solvent and cause intermixing.
• the content of the crosslinkable compound having two or more epoxy groups is larger than the above value, sufficient solubility in an alkaline developer used for developing a photoresist cannot be obtained. There is.
• the underlayer antireflection film-forming composition of the present invention contains an aromatic sulfonic acid ester compound.
• the aromatic sulfonic acid ester compound is not particularly limited.
• sulfonic acid alkyl ester compounds having an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a naphthacene ring, and a sulfonic acid aryl ester. Louis compound.
• examples thereof include sulfonic acid alkyl ester compounds and sulfonic acid aryl ester compounds having an aromatic hetero ring such as a pyridine ring, a furan ring, a quinoline ring, a thiophene ring, a pyrimidine ring, a quinoxaline ring, and a thiadiazole ring.
• the aromatic sulfonic acid ester compound contained in the composition for forming an underlayer antireflection film of the present invention can be obtained by a known method.
• an aromatic sulfonic acid ester compound can be obtained by reacting an aromatic sulfonyl chloride compound with an alcohol compound or a phenol compound in the presence of a base.
• aromatic sulfourekudo lydo compound examples thereof include benzene senorephonino rechloride, 4-tono reneno enore nonino rechloride, bistrobenzene senorephonyl chloride, 2 , 5 Diclonal benzene sulphonyl chloride, 1, 3 Benzene disreno phononyl chloride, 4 (2-phthalimido) phenol sulphonyl chloride, 2, 4, 6 Trimethylbenzen sulphonyl chloride, 1, 3, 5 Benzene tri Sulfo-chloride, 2, 3, 5, 6-tetramethylbenzene sulphonyl chloride, 4 (trifluoromethyl) benzene sulphonyl chloride, pentamethyl benzene sulphonyl chloride, 4-normal propyl benzene sulphonyl chloride, 4-e
• anthracenesulfuryl chloride compounds such as 2 anthracenesulfuryl chloride and 9 anthracenesulfuryl chloride
• fluorenesulfuryl chloride compounds such as fluorene 2,7 disulfol chloride are exemplified.
• Sulfonyl chloride compounds having an aromatic heterocycle The
• alcoholic compound and phenolic compound there can be used a compound capable of reacting with an aromatic sulfonyl chloride compound without particular limitation to give an aromatic sulfonic acid ester.
• Examples of the alcohol compound include methanol, ethanol, normal pentanol, cyclohexanol, cyclooctanol, decalin 2-ol, 2-ethyl-1-hexanol, 2-ethyl-1,3-hexanediol, 1, Examples include aliphatic alcohol compounds such as 2-cyclohexanediol, 2,2,2-trifluoroethanol, 1H, 1H-perfluoro-1-octanol, 1,2-cyclohexanedimethanol, and 2-tridecanol. .
• aromatic hydrocarbon ring or aromatic heterocycle such as benzyl alcohol, 9-hydroxymethylanthracene, phenylethyl alcohol, 1,2-benzenedimethanol, 2-hydroxymethylthiophene, and 2-naphthalenemethanol.
• Alcohol compound to be used is benzyl alcohol, 9-hydroxymethylanthracene, phenylethyl alcohol, 1,2-benzenedimethanol, 2-hydroxymethylthiophene, and 2-naphthalenemethanol.
• phenol compound examples include phenol, cresol, 2-naphthol, and hydroxyanthracene.
• Ar is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a nitro group, a cyano group, an amino group, a halogen group, a carboxyl group, and carbon.
• R and R are each a hydrogen atom or charcoal
• An alkyl group having 1 to 6 elementary atoms is represented. R and R are bonded to each other to form 3 to
• alkyl group examples include a methyl group, an ethyl group, an isopropyl group, a normal hexyl group, and a cyclopentyl group.
• alkoxy group examples include a methoxy group, an ethoxy group, an isopropyloxy group, a normal hexyloxy group, and a cyclopentyloxy group.
• alkoxycarbo yl group include a methoxy carbo ol group, an ethoxy carbo ol group, an isopropyloxy carbo ol group, and a cyclopentyloxy carbonyl group.
• Rings with 3 to 8 carbon atoms formed by R and R include cyclo A propyl ring, a cyclobutyl ring, a cyclohexyl ring, and the like.
• the halogen group includes a fluoro group, a black mouth group, a bromo group, and an iodine group.
• Examples of the compound having the structure represented by the formula (3) include a compound having a structure represented by the formula (44) and a compound represented by the formula (45):
• [0071] can be obtained by reaction with [0071].
• the compound having the structure represented by the formula (44) is an alcohol compound, and various alcohol compounds can be used.
• a compound having 2 to 4, or 2 to 3 structures represented by the formula (3) is used. can do.
• Such a compound can be obtained, for example, by reacting an alcohol compound having 2 to 4 structures of the formula (44) with a compound of the formula (45).
• Examples of the alcoholic compound having two to four structures of the formula (44) include ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, 1,2,3 propanetriol. , Diethylene glycol, triethylene glycol, pentaerythritol, 1,3 benzenedimethanol, 1,4 benzenedimethanol, 1,2 cyclohexanediol, 1,4-cyclohexanediol, 1,3 cyclopentanediol 1,2-dicyclohexyl lu, 1,2-ethanediol, 1,2-diphenyldiol, 1,2-ethanediol, 3,4 furandol, 1,4 dioxane 2,3 diol, and 1,4 dioxane 2, 5-diol, trimethylolpropane and the like.
• the compound of the formula (45) includes the benzenesulfonyl chloride compound, the na Examples thereof include a phthalene sulfochloride compound and the anthracene sulfochloride compound.
• a compound having two to four structures represented by the formula (3) is synthesized by reacting a compound having the structure represented by the formula (44) with a compound represented by the formula (45).
• the compound of the formula (45) can be used alone or in combination of two or more.
• the aromatic sulfonic acid ester compound used in the composition for forming an underlayer antireflection film of the present invention is not a compound that is easily decomposed by heat.
• the aromatic sulfonate ester compound used in the lower antireflection film-forming composition of the present invention has a thermal decomposition starting temperature of 100 ° C or higher, or 150 ° C or higher, or 200 ° C or higher, or An aromatic sulfonic acid ester compound having a temperature of 220 ° C or higher or 245 ° C or higher is preferably used.
• the thermal decomposition start temperature is the weight decrease start temperature obtained by TG measurement (thermogravimetry).
• aromatic sulfonic acid ester compound used in the composition for forming an underlayer antireflection film of the present invention include, for example, 1, 3 bis (p-toschioxy) propane, 1, 2 bis. (P—Tosioxy) ethane, 1,4 Diol o Tosyl 1,3— o—Isopropylidenethreitol, Triethylene glycol ditosylate, 2,3 Dihydroxybutane 1,4 Dirubis (p—Toluenesulfona 1), tetra (p-toluenesulfo-loxymethyl) methane, 1,2-propanediol p-tosylate, 1,2,4 tritosylbutanetriol, 2,3 butanediol p-tosylate, diethylene glycol di-p-tosylate, N, N-bis (2- (toxixy) ethyl) toluene-4-sulfonamide
• the aromatic sulfonic acid ester compound in the composition for forming a lower antireflection film of the present invention, can be used alone or in combination of two or more.
• the content thereof is, for example, 0.1 to 100 parts by mass of polyamic acid, LOO parts by mass, 1 to 50 parts by mass, 2 to 30 parts by mass, or 3 to 20 Parts by mass, and Is 5 to 15 parts by mass.
• the photoresist pattern may be large and undercut, and the dissolution rate of the lower antireflection film in the alkaline developer may be low. May cause problems in removing the lower antireflection coating.
• the underlayer antireflection film-forming composition of the present invention contains a photoacid generator.
• the photoacid generator is a compound that generates an acid by the action of light when the upper-layer photoresist is exposed by a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or the like. If so, V, deviation can also be used.
• Examples of such a photoacid generator include form salt compounds, sulfonimide compounds, and disulfonyl diazomethane compounds.
• salt salts include, for example, diphenol rhododone hexafluorophosphatate, diphenyl rhodonordotriolenoroleomethane sulphonate, diphenyl rhododomono nafnoroleolonorema.
• Norebutans norephonate diphenol-nouleo-muppernoleolol-normal octane sulfonate, diphenol-nodum camphor sulfonate, bis (4 —tert butylphenol) odonium camphor sulfonate and bis ( 4-tert-butyl) iodo-umtrifluoromethanesulfonate and other ododonium salt compounds; , Triphenylsulfo-mucamphor sulfonate and tri Et - Rusuruho - ⁇ beam triflate Ruo B sulfonyl Umushioi ⁇ of such as methane sulfonates.
• Examples of the sulfonimide compound include N- (trifluoromethanesulfo-loxy) succinimide, N- (nonafluoro-normalbutanesulfo-loxy) succinimide, N (camphorsulfo-loxy) succinimide and N (trifluoro Chloromethanesulfoloxy) naphthalimide and the like.
• disulfo-diazomethane compound examples include bis (trifluoromethylsulfo) diazomethane, bis (cyclohexylsulfo) diazomethane, bis (phenylsulfo) diazomethane, and bis (p toluenesulfo- ) Diazomethane, bis (2,4 dimethyl) Benzenesulfol) diazomethane, and methylsulfolulu p-toluenesulfol diazomethane.
• these photoacid generators can be used alone or in combination of two or more.
• the content of the photoacid generator is, for example, 0.01 to 20 parts by mass, or 0.05 to 10 parts by mass, for example, 0.1 to 100 parts by mass of the polyamic acid. Or 5 to 3 parts by mass, or 0.5 to 3 parts by mass.
• any solvent that can dissolve solids can be used.
• solvents include, for example, ethylene glycol monomethenore etherenole, ethylene glycol monomethenore etherenole, methinorecello sonoleb acetate, ethyl acetate sorbacetate, diethylene glycol monomethyl ether, diethylene glycol monorenoethylenore.
• Ether Propylene glycol, Propylene glycol monomethinole ether, Propylene glycol nomonomethino ethenore acetate, Propylene glycol propyl ether acetate, Toluene, Xylene, Methyleno ethinoreketone, Cyclopentanone, Cyclohexanone, 2 —Ethyl hydroxypropionate, 2-hydroxyethyl 2-methylpropionate, ethoxy ethoxy acetate, ethyl oxyacetate, 2-hydroxy 3-methylbutanoic acid Til, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, Butyl lactate, N, N di
• the prepared solution of the lower antireflection coating resin composition can be used after being filtered using a filter having a pore size of about 0.2 m to 0.05 m.
• the lower antireflective coating resin composition thus prepared is excellent in long-term storage stability at room temperature.
• composition for forming an underlayer antireflection film of the present invention may contain a light-absorbing compound.
• the light-absorbing compound is not particularly limited as long as it is a compound having absorption at the wavelength of light used for exposure of a photoresist.
• a compound having an aromatic ring structure such as an anthracene ring, naphthalene ring, benzene ring, quinoline ring, and triazine ring is preferably used.
• a naphthalene carboxylic acid ester compound can be used as the light-absorbing compound because it has a large absorption with respect to light having a wavelength of 248 nm.
• 2-hydroxy-3-naphthalenecarboxylic acid methyl ester 6-hydroxy-2-naphthalenecarboxylic acid benzyl ester, 3-hydroxy-7 methoxy-2-naphthalenecarboxylic acid propyl ester, 3,7 dihydroxy-2 naphthalenecarboxylic acid ethyl ester, etc. Is mentioned.
• Naphthalene carboxylic acid ester compounds other than the above are 1 naphthoic acid, 2 naphthoic acid, 1-hydroxy-2 naphthoic acid, 3 hydroxy-2 naphthoic acid, 3, 7-dihydroxy-2 naphthoic acid, 1,2 naphthalene dicarboxylic acid 1,3 naphthalene dicarboxylic acid, 1,4 naphthalene dicarboxylic acid, 1,5 naphthalene dicarboxylic acid, 1,6 naphthalene dicarboxylic acid, 1,7 naphthalene dicarboxylic acid, 1,8 naphthalene dicarboxylic acid, 2, 3 naphthalene Dicarboxylic acid, 2, 6 Naphthalenedicarboxylic acid, 6 Hydroxy 1 Naphthoic acid, 1-Hydroxy-2 Naphthoic acid, 3 Hydroxy-2 Naphthoic acid, 6 Hydroxy-2 Naphthoic acid, 1-brom
• naphthalenecarboxylic acid ester compounds obtained by the reaction of the naphthalenecarboxylic acid compound and the epoxy compound are mentioned. In this reaction, a reaction takes place between the carboxyl group of the naphthalene strength rubonic acid compound and the epoxy ring, and a naphthalene strength rubonic acid ester compound is obtained.
• Examples of the epoxy compound include tris (2,3 epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2 epoxy 1-4 (epoxyethyl) hexane, glycerol triglycidyl ether, diethylene glycol diglycidyl.
• Ether 2,6-diglycidylphenol-glycidyl ether, 1,1,3 tris (p- (2,3 epoxypropoxy) phenyl) propane, 1,2 dicyclohexylidenoleestenole, 1,2 cyclohexanedicarboxylic acid, 4 , 4'-methylenebis (N, N-diglycidyl dilin), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, trimethylol ethane triglycidyl ether, bisphenol A-diglycidyl ether, and Pentaerythritol polyglycidylate
• an epoxy compound the polymer containing the structure which has epoxy groups, such as glycidyl metatalylate, can be mentioned.
• the reaction of the naphthalenecarboxylic acid compound with the epoxy compound is carried out by reacting benzene, toluene, xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and N-methyl. It can be carried out in an organic solvent such as pyrrolidone.
• a quaternary ammonium salt such as benzyltriethylammonium chloride, tetraptylammonium chloride, and tetraethylammonium chloride can be used as a catalyst.
• the reaction temperature and reaction time depend on the compound used, concentration, etc. Force Reaction time 0.1 to: LOO time, reaction temperature 20 ° C to 200 ° C. When a catalyst is used, it can be used in the range of 0.001 to 30% by mass with respect to the total mass of the compound to be used.
• Np represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a hydroxyl group, or a carboxyl group.
• a naphthalene ring group which may be substituted with a group, a phenoxy group, a acetyl group or an alkoxycarbo group having 1 to 5 carbon atoms.
• the compound represented by the formula (48) can be obtained by reacting tris (2,3 epoxypropyl) isocyanurate with a naphthalenecarboxylic acid compound.
• tris (2,3 epoxypropyl) isocyanurate 1-hydroxy 2 naphthoic acid, 3 hydroxy 2 naphthoic acid, 3, 7 dihydroxy 2 naphthoic acid, 1,2 naphthalene Dicarboxylic acid, 1,4 Naphthalenedicarboxylic acid, 1,5 Naphthalene dicarboxylic acid, 2,3 naphthalene dicarboxylic acid, 2,6 naphthalene dicarboxylic acid, 6 hydroxy-1 naphthoic acid, 3 hydroxy-2 naphthoic acid, 1 bromo 2 hydroxy-3 naphthoic acid, 1-bromo 4-hydroxy-3 naphthoic acid, 1,6 Naphthalene carboxylic acid compounds such as -dibromo 2 hydroxy 3 naphthoic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3,5 dihydroxy-2 naphthoic acid, and 1,4-dihydroxy-2 naphth
• the absorbent compound can be used alone or in combination of two or more.
• a light-absorbing compound the content thereof is, for example, 1 to 300 parts by weight, or 3 to 200 parts by weight, for example 5 parts to 100 parts by weight of polyamic acid.
• ⁇ LOO parts by mass or 10-50 parts by mass.
• the solubility of the lower antireflection film in the alkaline developer may be lowered.
• the lower antireflection film-forming composition of the present invention can contain an aromatic carboxylic acid compound.
• the aromatic carboxylic acid compound By using the aromatic carboxylic acid compound, the dissolution rate of the lower antireflection film to be formed in the alkaline developer can be adjusted.
• the aromatic carboxylic acid compound is not particularly limited, and examples thereof include aromatic rings such as a benzene ring, naphthalene ring, anthracene ring, pyridine ring, thiophene ring, quinoxaline ring, quinoline ring, and benzothiazole ring.
• aromatic rings such as a benzene ring, naphthalene ring, anthracene ring, pyridine ring, thiophene ring, quinoxaline ring, quinoline ring, and benzothiazole ring.
• the aromatic carboxylic acid compound having the above can be used.
• aromatic carboxylic acid compounds include, for example, benzoic acid, pyromellitic acid, phthalic acid, trimeric acid, 4 sulfophthalic acid, benzenehexacarboxylic acid, 2, 3 naphthalene dicarboxylic acid, 3, 3 ', 4, 4,-biphenyl tetracarboxylic acid, 3, 3', 4, 4,-benzophenol tetracarboxylic acid, 3, 3 ', 4, 4, diphenyl ether tetracarboxylic acid, 3, 3 4,4'-diphenylsulfonetetracarboxylic acid, 2 naphthoic acid, thiophene 2 carboxylic acid and 9 anthracene carboxylic acid.
• Aromatic carboxylic acid compounds can be used.
• aromatic carboxylic acid compounds having a phenolic hydroxyl group include phenols such as hydroxybenzoic acid, 4-hydroxyphthalic acid, 3,4-dihydroxyphthalic acid, and 4,5-dihydroxyphthalic acid.
• Benzoic acid compounds having a reactive hydroxyl group and 2-hydroxy-3 naphthoic acid, 2-hydroxy-1 naphthoic acid, 8 hydroxy-1 naphthoic acid and 3,7 dihydroxy 2 naphthoic acid-containing naphthalene carboxylic acid Examples of such compounds are listed.
• the aromatic carboxylic acid compound can be used alone or in combination of two or more.
• the content thereof is, for example, 1 to: LOO parts by mass, or 3 to 50 parts by mass with respect to 100 parts by mass of polyamic acid. -30 mass parts, or 10-20 mass parts. If the content of the aromatic carboxylic acid compound is larger than the above value !, the solubility of the lower antireflection film in the alkaline developer becomes too high, which may cause problems such as poor pattern shape.
• the lower-layer antireflection film-forming composition of the present invention may further contain a surfactant, a rheology adjusting agent, an adhesion aid, and the like, if necessary.
• surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene ethylene ether, polyoxyethylene octyl phenol ether, Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, resonatebitan monostearate, sorbitan monooleate, Sorbitan fatty acid esters such as sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxy Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-
• the amount of these surfactants to be added is generally 0.2% by mass or less, preferably 0.1% by mass or less, based on all components of the composition for forming an underlayer antireflection film of the present invention.
• These surfactants may be added singly or in combination of two or more.
• a semiconductor substrate for example, a silicon Z-dioxide-silicon-coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, etc.
• the lower-layer antireflection film-forming composition of the invention is applied and then baked to form a lower-layer antireflection film.
• medium strength of firing temperature of 80 ° C to 300 ° C and firing time of 0.3 to 60 minutes is appropriately selected.
• the dissolution rate in the alkaline developer used to develop the lower antireflection film and photoresist formed is 0. Inn! ⁇ 50 nm, preferably 0.2 nm to 40 nm per second, more preferably 0.3 ⁇ ! ⁇ 20nm. If the dissolution rate is smaller than this, the time required to remove the lower antireflection film becomes longer, leading to a decrease in productivity. If the dissolution rate is higher than this, the lower antireflection film below the unexposed portion of the photoresist also dissolves, and as a result, a photoresist pattern may not be formed.
• the lower antireflection film formed from the lower antireflection film-forming composition of the present invention can control the dissolution rate of the lower antireflection film in an alkaline developer by changing the baking conditions at the time of formation. it can. In the case of a certain baking time, the lower the antireflection film having a lower dissolution rate in the alkaline developer, the higher the baking temperature.
• a photoresist layer is formed on the lower antireflection film.
• the formation of the photoresist layer can be performed by a general method, that is, by applying a photoresist solution onto the lower antireflection film and baking.
• the photoresist formed on the lower antireflection film of the present invention is used for exposure. As long as it is sensitive to light, there is no particular limitation, and a shift between negative and positive photoresists can be used. Examples of such photoresists include novolak resin, 1,2-naphthoquinonediazide sulfonate ester and powerful positive photoresist, a binder having a group that decomposes with an acid to increase the alkali dissolution rate, and a photoacid generator.
• Chemically amplified photoresist that can be decomposed by acid chemically amplified photoresist composed of a low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator.
• chemically amplified photoresists composed of a photoacid generator and a low molecular weight compound that decomposes with a noinder having a group that increases the rate and an acid to increase the alkali dissolution rate of the photoresist.
• trade name A PEX-E manufactured by Shipley Co., Ltd. trade name PAR710 manufactured by Sumitomo Chemical Co., Ltd.
• trade name SE PR430 manufactured by Shin-Etsu Chemical Co., Ltd. trade name SE
• a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 ⁇ m), or the like can be used.
• post exposure bake can be performed.
• Alkaline developers used for developing photoresists include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, hydroxide tetramethylammonium, water.
• alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, hydroxide tetramethylammonium, water.
• examples include aqueous solutions of quaternary ammonium hydroxides such as tetraethyl ammonium oxide and choline, and alkaline aqueous solutions such as aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine.
• a surfactant or the like can be added to these developers.
• the development conditions are appropriately selected from a temperature of 5 ° C to 50 ° C and a time of 10 to 300 seconds.
• bottom anti-reflective coating which is bottom anti-reflective coating forming composition mosquito ⁇ et form of the invention, Mizusani ⁇ tetramethylammonium of 2.38 mass 0/0, which is widely used as the alkaline developer - Development can be easily carried out at room temperature using an aqueous solution of sulfur.
• the lower antireflection film of the present invention is a layer for preventing the interaction between the semiconductor substrate and the photoresist, the material used for the photoresist, or the adverse effect on the substrate of the substance generated during exposure to the photoresist. As a layer for preventing diffusion of the material generated from the substrate during heating and baking into the upper photoresist, and a noria layer for reducing the bisting effect of the photoresist layer by the semiconductor substrate dielectric layer It can also be used.
• a lower antireflection film was formed in the same manner as described above at a firing temperature of 170 ° C and 180 ° C. Then, it was confirmed that these lower antireflection films were insoluble in ethyl lactate and propylene glycol monomethyl ether acetate.
• the dissolution rate of the lower antireflection film in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution: Tokyo Oka Kogyo Co., Ltd., product name NMD-3) was measured using a resist developer analyzer (litho Measured using Tech Japan Co., Ltd.
• the dissolution rate of the lower antireflection film formed at a firing temperature of 175 ° C. and a firing time of 1 minute was 1.74 nm per second.
• the dissolution rate of the lower antireflection film formed at a firing temperature of 170 ° C and a firing time of 1 minute is 2.35 nm per second, and the dissolution rate of the lower antireflection film formed at a firing temperature of 180 ° C and a firing time of 1 minute is 1.48 nm per second.
• the lower layer antireflection film-forming composition solution [1] was applied onto a silicon wafer substrate using a spinner and then baked on a hot plate at 175 ° C for 1 minute to prevent the lower layer antireflection film with a thickness of 40 nm. A film was formed. A positive photoresist for ArF was formed on the lower antireflection film, and exposed with an ArF excimer laser (wavelength: 193 nm) through a mask set to form a 7 Onm line Z space pattern. After exposure and heating at 110 ° C.
• Og and solution containing light-absorbing compound [a] 4. 15 g, 4, 4, 1 methylene bis (N, N-diglycidyl dilin) 1. 13 g, 3, 7-dihydroxynaphthoic acid 0.825 g, propylene glycol monomethyl ether 82.8 g, propylene glycol monomethyl ether acetate 127 g, and cyclohexanone 10.
• Og was added and stirred at room temperature for 30 minutes to form a lower antireflection film composition
• a product solution [2] was prepared.
• the lower antireflection film-forming composition solution [2] was applied onto a silicon wafer substrate using a spinner, and then baked on a hot plate at 175 ° C. for 1 minute to form a lower antireflection film having a thickness of 40 nm. Formed.
• the obtained lower antireflection film was insoluble in propylene glycol, lactate ethyl and propylene glycol monomethyl ether acetate.
• the refractive index (n value) at a wavelength of 248 nm is 1.82
• the attenuation coefficient (k value) is 0.42
• the refractive index (n value) at a wavelength of 193 nm is The coefficient of attenuation was 1.51, and the attenuation coefficient (k value) was 0.42.
• a lower antireflection film was similarly formed at a firing temperature of 170 ° C and 180 ° C. Then, it was confirmed that these lower antireflection films were insoluble in ethyl acetate and propylene glycol monomethyl ether acetate.
• the dissolution rate of the lower antireflection film in 2.38% tetramethylammonium hydroxide aqueous solution (trade name NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used as a resist development analyzer (Risotech Japan Co., Ltd.) ).
• the dissolution rate of the lower antireflection film formed at a firing temperature of 175 ° C and a firing time of 60 seconds was 2.40 nm per second.
• the dissolution rate of the lower antireflection film formed at a firing temperature of 170 ° C and a firing time of 1 minute was 2.65 nm per second
• the dissolution rate of the lower antireflection film formed at a firing temperature of 180 ° C and a firing time of 1 minute. was 2.03 ⁇ m per second.
• the lower antireflection film forming composition solution [2] was applied onto a silicon wafer substrate using a spinner and then baked on a hot plate at 175 ° C for 1 minute to prevent the lower layer antireflection film with a thickness of 40 nm. A film was formed. A positive photoresist for ArF is formed on the lower antireflection film, and the ArF is passed through a mask set to form a 7 Onm line Z space pattern. Exposed with an excimer laser (wavelength 193 nm). After exposure and heating at 110 ° C.
• this lower-layer antireflection film-forming composition solution [3] After applying this lower-layer antireflection film-forming composition solution [3] onto a silicon wafer substrate using a spinner, it was baked on a hot plate at 175 ° C. for 1 minute to form a lower-layer antireflection film having a thickness of 40 nm. Formed.
• the obtained lower antireflection film was insoluble in propylene glycol, lactate ethyl and propylene glycol monomethyl ether acetate.
• the refractive index (n value) at a wavelength of 248 nm is 1.80
• the attenuation coefficient (k value) is 0.44
• the refractive index (n value) at a wavelength of 193 nm is 1. 50 and the damping coefficient (k value) was 0.44.
• an antireflection film was similarly formed at a firing temperature of 170 ° C and 180 ° C. Then, it was confirmed that these lower antireflection films were insoluble in ethyl lactate and propylene glycol monomethyl ether acetate.
• the dissolution rate of the lower antireflection film in 2.38% tetramethylammonium hydroxide aqueous solution (trade name NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used as a resist development analyzer (Risotech Japan Co., Ltd.) ).
• the dissolution rate of the lower antireflection film formed at a firing temperature of 175 ° C and a firing time of 1 minute was 2. OOnm per second.
• the dissolution rate of the lower antireflection film formed at a baking temperature of 170 ° C. and a baking time of 1 minute was 2.35 nm per second.
• the dissolution rate of the lower antireflection film formed at a deposition temperature of 180 ° C. and a baking time of 1 minute was 1.8 2 nm per second.

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