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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers

Definitions

• the present invention relates to a pattern formation method and a treatment solution for a metal compound-containing film.
• the size of individual structures on a semiconductor device chip is approximately 22 nm or less, and in some cases less than 10 nm.
• the photolithography process for forming these microstructures typically uses ultraviolet (UV) light with a wavelength of 193 nm for exposure.
• UV ultraviolet
• the wavelength of this light is already significantly larger than the desired pattern size to be formed on the semiconductor substrate.
• complex high-resolution techniques such as multi-patterning are required to achieve pattern sizes smaller than the wavelength of light. Therefore, it is very important to develop lithography techniques that use extremely short wavelength light such as extreme ultraviolet (EUV) light with a wavelength of about 10 to 15 nm (e.g., 13.5 nm) or particle beams such as electron beams (EB).
• EUV extreme ultraviolet
• EB electron beams
• the resist film in photolithography processes using EUV, it is difficult to apply chemically amplified organic resists due to the absorption characteristics of the resist composition. Furthermore, in order to impart sufficient etching resistance to a patterned resist film formed using an organic resist, the resist film must be made thick. In this case, the patterned resist film has a high aspect ratio, which poses a high risk of pattern collapse. For these reasons, there is a demand for a method for forming a resist film that can be well patterned using EUV (extreme ultraviolet) or electron beam lithography and that exhibits excellent etching resistance even when thin.
• EUV extreme ultraviolet
• Patent Documents 1 and 2, etc. metal compound-containing resists using tin compounds and the like have been proposed (for example, Patent Documents 1 and 2, etc.).
• the present invention was made in consideration of the above-mentioned conventional situation, and aims to provide a method for forming a pattern of a metal compound-containing film, and a treatment liquid that can be suitably used for forming a pattern of a metal compound-containing film.
• the inventors have conducted extensive research to solve the above problems, and have found that after exposing a metal compound-containing film, the unexposed areas of the metal compound-containing film can be selectively reduced and a pattern can be formed by using one or more solvents selected from the group consisting of: (1) a benzene ring in which one or more hydrogen atoms are substituted with a polar substituent; (2) a 5- or 6-membered aromatic heterocycle in which one or more hydrogen atoms may be substituted with a polar substituent; (3) a 5- or 6-membered hydrocarbon ring having one or more double bonds in the ring and at least one or more hydrogen atoms being substituted with a polar substituent, or having a carbonyl group in the ring and at least one or more hydrogen atoms being substituted with a polar substituent; and (4) a 5- or 6-membered non-aromatic heterocycle in which at least one or more hydrogen atoms are substituted with a polar substituent, or having a total of two or
• the inventors have found that after exposing a metal compound-containing film, the unexposed areas of the metal compound-containing film can be selectively reduced and a pattern can be formed by using one or more solvents selected from the group consisting of: (1) a benzene ring in which one or more hydrogen atoms are substituted with a polar substituent; (2) a 5- or 6-membered aromatic heterocycle in which one or more hydrogen atoms are substituted with a polar substituent; (3) a 5- or 6-membered non-aromatic heterocycle in which at least one hydrogen atom is substituted with a polar substituent;
• a pattern forming method including a step of exposing a metal compound-containing film to light and a step of treating the exposed metal compound-containing film with a treatment liquid
• the treatment liquid is (1) a benzene ring in which one or more hydrogen atoms are replaced by a polar substituent; (2) a 5- or 6-membered aromatic heterocycle in which one or more hydrogen atoms may be substituted with a polar substituent; (3) A 5- or 6-membered hydrocarbon ring having one or more double bonds in the ring and at least one or more hydrogen atoms being substituted with a polar substituent, or having a carbonyl group in the ring and at least one or more hydrogen atoms being substituted with a polar substituent, and (4) A 5- or 6-membered non-aromatic heterocycle in which at least one hydrogen atom is substituted with a polar substituent, or which has a total of two or more heteroatoms or carbonyl groups in the
• a pattern forming method including the steps of forming a metal compound-containing film using a metal compound-containing film-forming composition, exposing the metal compound-containing film to light, and treating the exposed metal compound-containing film with a treatment liquid,
• the treatment liquid is (1) a benzene ring in which one or more hydrogen atoms are replaced by a polar substituent; (2) a 5- or 6-membered aromatic heterocycle in which one or more hydrogen atoms may be substituted with a polar substituent; (3) A 5- or 6-membered hydrocarbon ring having one or more double bonds in the ring and at least one or more hydrogen atoms being substituted with a polar substituent, or having a carbonyl group in the ring and at least one or more hydrogen atoms being substituted with a polar substituent, and (4) A 5- or 6-membered non-aromatic heterocycle in which at least one hydrogen atom is substituted with a polar substituent, or which has a total of two or more heteroatoms or carbon
• the treatment liquid further contains 1 to 80 mass % of a second solvent different from the first solvent.
• the second solvent is one or more solvents selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and water.
• the metal compound-containing film is a metal compound-containing film containing a metal element of Groups 3 to 7.
• the metal compound is a polyoxometalate.
• the pattern formation method according to [6], wherein the polyoxometalate is a polyoxomolybdate, a polyoxotungstate, a polyoxovanadate, a polyoxoniobate, or a polyoxotantalate.
• the pattern forming method according to [6], wherein the polyoxometalate is an onium salt.
• the pattern formation method according to [8], wherein the onium salt is an ammonium salt, a sulfonium salt, or an iodonium salt.
• the pattern forming method according to [1], wherein the exposing step is a step of exposing to EUV or an electron beam.
• a metal compound-containing film treatment solution comprising at least 20% by mass of a first solvent which is one or more solvents selected from the group consisting of: (1) a benzene ring in which one or more hydrogen atoms are substituted with a polar substituent; (2) a 5- or 6-membered aromatic heterocycle in which one or more hydrogen atoms may be substituted with a polar substituent; (3) a 5- or 6-membered hydrocarbon ring having one or more double bonds in the ring and at least one of the hydrogen atoms being substituted with a polar substituent, or having a carbonyl group in the ring and at least one of the hydrogen atoms being substituted with a polar substituent; and (4) a 5- or 6-membered non-aromatic heterocycle in which at least one hydrogen atom is substituted with a polar substituent, or having a total of two or more heteroatoms or carbonyl groups in the ring and at least one of the hydrogen atoms being substituted with a polar substituent
• the second solvent is one or more solvents selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, and water.
• the metal compound-containing film treatment liquid according to [11] which is a polyoxometalate-containing film treatment liquid.
• the present invention provides a method for forming a pattern of a metal compound-containing film, and a treatment liquid that can be suitably used in forming a pattern of a metal compound-containing film. Furthermore, the treatment liquid of the present invention can selectively reduce the film in the unexposed areas of the metal compound-containing film, and can be suitably used as a treatment liquid for metal compound films, particularly as a treatment liquid for polyoxometalate-containing films.
• the pattern formation method includes the steps of forming a metal compound-containing film on a substrate using a metal compound-containing film-forming composition, exposing the metal compound-containing film to light, and treating the exposed metal compound-containing film with a treatment liquid, wherein the treatment liquid contains 20% by mass or more of a first solvent which is any one of the following (1) to (4): (1) A benzene ring in which one or more hydrogen atoms are replaced by a polar substituent; (2) A 5- or 6-membered aromatic heterocycle in which one or more hydrogen atoms may be replaced by a polar substituent; (3) A 5- or 6-membered hydrocarbon ring having one or more double bonds in the ring and at least one or more hydrogen atoms replaced by a polar substituent, or having a carbonyl group in the ring and at least one or more hydrogen atoms may be replaced by a polar substituent; (4) A 5- or 6-membered non-aromatic heterocycle in which at least one hydrogen atom is replaced by a first solvent which is any one
• the metal compound-containing film-forming composition according to the present embodiment contains a metal compound.
• the metal compound is not particularly limited, and may be a metal atom or a metal of a metal element in Groups 3 to 16 of the long-form periodic table. ions, metal oxides of said metal atoms or metal ions, or those containing bonds that are ionic, coordinate or covalently bonded to said metal atoms, metal ions or metal oxides can be used. .
• metal elements of Groups 3 to 16 in the long-form periodic table can be used.
• metal elements in Groups 3 to 16 of the long-form periodic table include metal elements in Group 3 such as scandium (Sc), yttrium (Y), lanthanum (La), and cerium (Ce); Metal elements of Group 4 such as Ti, Zr, and Hf; metal elements of Group 5 such as vanadium (V), niobium (Nb), and tantalum (Ta); chromium (Cr), Metal elements of Group 6 such as molybdenum (Mo) and tungsten (W); metal elements of Group 7 such as manganese (Mn) and rhenium (Re); iron (Fe), ruthenium (Ru), and osmium (Os) Metal elements of Group 8 such as cobalt (Co), Metal elements of Group 9 such as rhenium (Rh) and iridium (Ir); metal
• Group 11 metal elements such as zinc (Zn), cadmium (Cd), and mercury (Hg);
• Group 12 metal elements such as aluminum (Al), gallium (Ga), and indium (In Group 13 metal elements such as thallium (Tl);
• Group 14 metal elements such as germanium (Ge), tin (Sn), lead (Pb);
• Group 15 metal elements such as antimony (Sb), bismuth (Bi), etc.
• Metal elements of Group 15; metal elements of Group 16 such as tellurium (Te), etc.
• the metal compound may contain one of the above metal elements alone or a combination of two or more of them.
• the metal element contained in the metal compound among the above metal elements, it is preferable to use a metal element in the 4th to 6th periods of Groups 3 to 16.
• a tin compound or the like can be suitably used.
• the tin compound may cause problems such as contamination of equipment due to residues generated during coating processing, and the toxicity of the tin compound itself.
• the metal oxide of the metal atom or metal ion of the above metal element is not particularly limited, and any known or commonly used substance can be used.
• the metal oxide that can be used include scandium oxide (Sc 2 O 3 ), yttrium oxide (Y 2 O 3 ), titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), hafnium oxide (HfO 2 ), vanadium oxide (V 2 O 5 ), niobium oxide (Nb 2 O 5 ), tantalum oxide (Ta 2 O 5 ), chromium oxide (CrO 3 ), molybdenum oxide (MoO 3 ), tungsten oxide (WO 3 ), aluminum oxide (Al 2 O 3 ), gallium oxide (Ga 2 O 3 ), indium oxide (In 2 O 3 ), germanium dioxide (GaO 2 ), tin oxide (SnO), and antimony trioxide (Sb 2 O 3 ).
• polyoxometalates As the metal oxide, polyoxometalates (polyacid salts) can be preferably used. Polyoxometalates are anionic metal oxide clusters represented by the general formula [M x O y ] n- (wherein x, y, and n are all natural numbers).
• the metal atom M constituting the polyoxometalate is called a polyatom, and examples thereof include Mo (hexavalent or pentavalent), W (hexavalent or pentavalent), V (pentavalent), Nb (pentavalent), and Ta (pentavalent).
• Polyoxometalates can be broadly classified into isopolyoxometalates constituted by the above-mentioned polyatom M and an oxyacid, and heteropolyoxometalates ([ XwMxOy ] n- (wherein w , x, y , and n are all natural numbers)) that contain, in addition to the above-mentioned polyatom M and oxygen, different types of atoms X (for example, heteroatoms X include P5+, Si4 +, Ge4+, B3 + , etc.).
• Examples of the isopolyoxometalate include salts of isopolyoxomolybdic acid, isopolyoxotungstic acid, isopolyoxovanadic acid, isopolyoxoniobic acid, and isopolyoxotantalic acid.
• Examples of the isopolyoxomolybdic acid include [MoO 4 ] 2- , [Mo 7 O 24 ] 6- , and [Mo 8 O 26 ] 4- .
• Examples of the isopolyoxotungstic acid include [W 4 O 13 ] 2 ⁇ , [W 5 O 16 ] 2 ⁇ , [W 6 O 19 ] 2 ⁇ , [W 7 O 22 ] 2 ⁇ , [W 7 O 24 ] 6 ⁇ , [H z W 12 O 40 ] -(8-z) (wherein z represents an integer of 1 to 4), [W 10 O 32 ] 4 ⁇ , [H 4 W 11 O 38 ] 6 ⁇ , [H 7 W 11 O 40 ] 7 ⁇ , [HW 5 O 19 ] 7 ⁇ , [H 3 W 11 O 22 ] 5 ⁇ and the like.
• Examples of the isopolyoxovanadic acid include [V 4 O 12 ] 4 ⁇ and [V 10 O 28 ] 6 ⁇ .
• Examples of the isopolyoxoniobic acid include [Nb 6 O 19 ] 8 ⁇ and [Nb 10 O 28 ] 6 ⁇ .
• Examples of the isopolyoxotantalic acid include [Ta 6 O 19 ] 8 ⁇ and [Ta 8 O 21 ] 2 ⁇ .
• the above-mentioned isopolyoxomolybdic acid, isopolyoxotungstic acid, isopolyoxovanadic acid, isopolyoxoniobic acid, and isopolyoxotantalic acid include various isomers.
• heteropolyoxometalate examples include salts of heteropolyoxomolybdic acid, heteropolyoxotungstic acid, heteropolyoxovanadic acid, heteropolyoxoniobic acid, and heteropolyoxotantalic acid.
• heteropolyoxomolybdic acid examples include phosphomolybdic acid, silicomolybdic acid, boromolybdic acid, phosphotungstomolybdic acid, cobalt molybdic acid, arsenic molybdic acid, germanium molybdic acid, etc.
• heteropolyoxotungstic acid examples include phosphotungstic acid, silicotungstic acid, borotungstic acid, cobalt tungstic acid, arsenic tungstic acid, germanium tungstic acid, etc.
• heteropolyoxovanadic acid examples include phosphomolybdovanadic acid, phosphomolybdotungstomolybdic acid, boromolybdovanadic acid, boromolybdotungstovanadic acid, etc.
• the above-mentioned heteropolyoxomolybdic acid, heteropolyoxotungstic acid, heteropolyoxovanadic acid and the like include Keggin type, Dawson type, Anderson type and defective species and isomers thereof.
• the type of salt of a polyacid salt is not particularly limited, and may be a salt with a proton, an onium cation (for example, an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic quaternary ammonium cation, an organic phosphonium cation, etc.), an alkali metal ion, etc.
• an onium cation for example, an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic quaternary ammonium cation, an organic phosphonium cation, etc.
• the type of salt of a polyacid salt is preferably a salt with an onium cation, and among these, a salt with an organic sulfonium cation, an organic iodonium cation, or an organic quaternary ammonium cation is more preferable.
• organic sulfonium cation is not particularly limited, and any known and commonly used organic sulfonium cation can be used.
• organic sulfonium cations include organic sulfonium cations represented by formula (I).
• R 1A , R 1B and R 1C each independently represent a C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group;
• the hydrogen atoms contained in R 1A , R 1B and R 1C are, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group
• R 1A , R 1B and R 1C are each preferably independently a C 6-18 aryl group which may have a substituent.
• the substituent of the C 6-18 aryl group is preferably a halogen atom, a haloalkyl group, a hydroxy group, a nitro group, a cyano group or a C 1-12 hydrocarbylthio group which may have a substituent, more preferably a halogen atom, a C 1-4 haloalkyl group or a nitro group.
• organic sulfonium cations include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalene-1-yl)hexahydrothiopyrylium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1- Phenylhexahydrothiopyrylium cation, (
• the organic iodonium cation is not particularly limited, and any known and commonly used organic iodonium cation can be used.
• an organic iodonium cation represented by formula (II) can be used.
• R 2A and R 2B each independently represent a C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group;
• the hydrogen atoms contained in R 2A and R 2B are, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g
• R 2A and R 2B are each preferably independently a C 6-18 aryl group which may have a substituent.
• the substituent of the C 6-18 aryl group is preferably a halogen atom, a haloalkyl group, a hydroxy group, a nitro group, a cyano group, a C 1-12 hydrocarbyl group which may have a substituent, a C 1-12 hydrocarbyloxy group, a C 1-12 hydrocarbylcarbonyl group, a C 1-12 hydrocarbylcarbonyloxy group, a C 1-12 hydrocarbyloxycarbonyl group, or a C 1-12 hydrocarbyloxycarbonyloxy group, and is preferably a halogen atom, a C 1-4 haloalkyl group, a nitro group, a C 1-8 hydrocarbyl group, or a C 1-8 hydrocarbyloxy group.
• organic iodonium cations include ethynyl(phenyl)iodonium cation, bis(pyridine)iodonium cation, bis(2,4,6-trimethylpyridine)iodonium cation, diphenyliodonium cation, bis(4-(t-butyl)phenyl)iodonium cation, (2-carboxyphenyl)(phenyl)iodonium cation, (4-nitrophenyl)(phenyl)iodonium cation, (3-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, bis(4-fluorophenyl)iodonium cation, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium cation,
• the organic quaternary ammonium cation is not particularly limited, and any known and commonly used cation can be used.
• An example of the organic quaternary ammonium cation is the organic quaternary ammonium cation represented by formula (III).
• R 3A , R 3B , R 3C and R 3D each independently represent a C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group;
• the hydrogen atoms contained in R 3A , R 3B , R 3C and R 3D are, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d)
• R 3A , R 3B , R 3C and R 3D are each preferably a C 1-18 hydrocarbyl group which may have a substituent, and more preferably a C 1-12 alkyl group, a C 1-12 alkenyl group, a C 1-12 alkynyl group or a C 1-12 alicyclic group.
• organic quaternary ammonium cations include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, tetraheptylammonium cation, trimethylethylammonium cation, dimethyldiethylammonium cation, dimethylethylpropylammonium cation, methylethylpropylbutylammonium cation, trimethylphenylammonium cation, triethylhexylammonium cation, triethylcyclohexylammonium cation, and dodecyltrimethylammonium cation.
• Polyacid salts have characteristics such as high thermal stability, oxidation resistance, high acid strength/oxidizing power, and reversible multi-electron redox ability, and examples of the synthesis and use of actinic ray- or radiation-sensitive polyoxometalates have been reported (e.g., JP-A-63-113452, JP-A-59-154089, JP-A-58-180400, etc.).
• polyacid salts are salts of anionic polynuclear metal oxoclusters, they have poor solubility in solvents, and it has been difficult to provide a difference in solubility between the areas exposed to actinic ray or radiation and the areas not exposed to it.
• the treatment liquid according to the present embodiment described later it is possible to form a good pattern even when the metal compound-containing film-forming composition contains a polyacid salt as a metal compound.
• the content of the metal compound is not particularly limited and can be appropriately selected depending on the type of metal compound, the application, etc.
• the content of the metal compound in the metal compound-containing film-forming composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, when the metal compound-containing film-forming composition is taken as 100 parts by mass.
• the metal compound-containing film-forming composition may contain an organic solvent, an inorganic filler, a quencher, a leveling agent, a surfactant, and the like, as required.
• the organic solvent is not particularly limited as long as it can dissolve the metal compound and form a metal compound-containing film on the substrate.
• organic solvents include halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane; alcohols such as methanol, ethanol, iso-propanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, and diacetone alcohol; ethers such as propylene glycol monomethyl ether (PGME), diethyl ether, tetrahydrofuran, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; ethyl acetate, acetic acid, and the like.
• halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane
• alcohols such as
• suitable solvents include esters such as n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester, and ethyl acetoacetate; lactones such as ⁇ -butyrolactone (GBL) and ⁇ -caprolactone; lactams such as N-methylpyrrolidone, and nitriles such as acetonitrile and propionitrile; cyclic or acyclic carbonates such as dimethyl carbonate, ethylene carbonate, propylene carbonate, and diphenyl carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; and water.
• esters such as n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester, and ethyl
• organic solvents may be used alone or in combination of two or more.
• PGME, PGMEA, EL, GBL, methanol, water, or a combination thereof is preferably used.
• the pattern forming method includes a step of forming a metal compound-containing film on a substrate using a metal compound-containing film forming composition.
• the substrate used in this embodiment is not particularly limited, and any known and commonly used substrate may be used.
• a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed may be used.
• the material of the substrate is not particularly limited, and examples thereof include substrates made of metals such as silicon wafers, copper, chromium, iron, and aluminum, and substrates made of inorganic substances such as glass, titanium oxide, and silicon dioxide.
• the size, shape, etc. of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or may be a thin-plate-shaped substrate, etc.
• the surface of the substrate may be subjected to a surface treatment as necessary.
• the surface of the substrate can be treated with a silane coupling agent capable of reacting with the hydroxyl groups, thereby changing the surface layer of the substrate from hydrophilic to hydrophobic, thereby improving the adhesion between the substrate and the metal compound-containing film.
• the silane coupling agent include hexamethyldisilazane (HMDS).
• the method of forming the metal compound-containing film on the substrate is not particularly limited, and can be any known and commonly used method.
• the film forming method for example, the CVD method (chemical vapor deposition method) such as thermal CVD, plasma CVD, photo CVD, etc., and the PVD method (physical vapor deposition method) such as vacuum deposition, plasma-assisted deposition, sputtering, ion plating, etc. can be used as the dry method.
• the coating method such as spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, screen printing, etc. can be used as the wet method.
• a method for forming a metal compound-containing film on a substrate using the metal compound-containing film-forming composition according to this embodiment from the viewpoint of forming a uniform film thickness, etc., it is preferable to use a wet method such as spin coating or screen printing, and it is more preferable to use spin coating.
• the method for drying the metal compound-containing film after it has been formed on the substrate is not particularly limited, and can be, for example, by using a heating device such as a hot plate (post applied bake (PAB)), a pressure reducing device, or the like.
• the baking conditions are not particularly limited and can be appropriately set depending on the type, application, etc. of the metal compound-containing film.
• the baking temperature is preferably 100 to 300° C., more preferably 150 to 250° C., and even more preferably 170 to 230° C.
• the baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.
• the thickness of the metal compound-containing film after drying is not particularly limited, but is preferably 0.5 to 100 nm, more preferably 1 to 75 nm, and even more preferably 1 to 60 nm.
• the pattern forming method according to this embodiment includes a step of exposing the formed metal compound-containing film to light.
• an ArF exposure device In the exposure process of the metal compound-containing film, an ArF exposure device, an electron beam lithography device, an EUV exposure device, or the like can be used as the exposure device.
• exposure may be performed through a mask (mask pattern) on which a predetermined pattern is formed, or selective exposure may be performed by lithography using direct irradiation with an electron beam without using a mask pattern.
• the wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser (wavelength 193 nm), KrF excimer laser (248 nm), F2 excimer laser (wavelength 157 nm), EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays may be used.
• the exposure dose onto the metal compound-containing film is preferably 1 to 100 mJ/cm 2 , and more preferably 20 to 60 mJ/cm 2 , in the case of an ArF excimer laser or a KrF excimer laser.
• the exposure dose is preferably 0.1 to 20 mJ/cm 2 , and more preferably 3 to 15 mJ/cm 2 .
• exposure is preferably performed at 50 kV with a dose of 3 ⁇ C/cm 2 to 2 mC/cm 2 , and more preferably with a dose of 10 ⁇ C/cm 2 to 1.5 mC/cm 2 .
• a baking (post-exposure bake (PEB)) process may be performed.
• the baking temperature is preferably 120 to 300°C, more preferably 150 to 250°C, and even more preferably 170 to 230°C, using a heating device such as a hot plate.
• the baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.
• the pattern formation method according to this embodiment includes a step of treating the exposed metal compound-containing film with a treatment liquid.
• C 1-4 refers to the number of carbon atoms in the core group.
• C 1-4 alkyl group refers to a straight or branched alkyl group having 1 to 4 carbon atoms.
• the "C 1-4 alkyl group” is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a t-butyl group.
• C 2-4 alkenyl group refers to an alkenyl group having one double bond in a "C 1-4 alkyl group” having 2 or more carbon atoms.
• the " C2-4 alkenyl group” is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a 1-propenyl group, an isopropenyl group (1-methylvinyl group), a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group.
• C 2-4 alkynyl group refers to an alkynyl group having one triple bond in a "C 1-4 alkyl group” having 2 or more carbon atoms.
• the "C 2-4 alkynyl group” is not particularly limited, and examples thereof include an ethynyl group, a 1-propynyl group, and a 2-propynyl group.
• a "C 3-4 alicyclic group” refers to a cyclic hydrocarbon group having 3 to 4 carbon atoms. Alicyclic groups include cycloalkyl groups, cycloalkenyl groups, and the like. The “C 3-4 alicyclic group” is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, and the like.
• 5- or 6-membered aromatic heterocycle refers to a monocyclic 5- or 6-membered aromatic heterocycle containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and an oxygen atom.
• the "5- or 6-membered aromatic heterocycle” is not particularly limited, and examples thereof include 5-membered aromatic heterocycles such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, oxazole, isoxazole, isothiazole, thiazole, 1,2,5-oxadiazole, 1,2,3-oxadiazole, 1,3,4-thiadiazole, and 1,2,5-thiadiazole; and 6-membered aromatic heterocycles such as pyridine, pyridazine, pyrimidine, 1,2,4-triazine, and 1,3,5-triazine.
• 5-membered aromatic heterocycles such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, oxazole, is
• a "5- or 6-membered hydrocarbon ring” refers to a cyclic hydrocarbon group having 5 or 6 carbon atoms, which may be saturated or unsaturated.
• the "5- or 6-membered hydrocarbon ring” is not particularly limited, and examples thereof include cyclopentane, cyclopentene, cyclopentanone, cyclohexane, cyclohexene, cyclohexanone, and the like.
• the term "5- or 6-membered non-aromatic heterocycle” refers to a 5- or 6-membered non-aromatic heterocycle containing one or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and may be saturated or partially unsaturated.
• the "5- or 6-membered non-aromatic heterocyclic group” is not particularly limited, and examples thereof include 5-membered non-aromatic heterocycles such as pyrrolidine, 3-pyrroline, pyrazolidine, imidazolidine, 2-pyrazoline, 2-imidazoline, tetrahydrofuran, 1,3-dioxolane, tetrahydrothiophene, 1,2-oxathiolane, 1,3-oxathiolane, 2,4-thiazolidinedione, succinimide, 2-oxazolidone, hydantoin, ⁇ -butyrolactone, and ⁇ -lactam; piperidine, 6-membered non-aromatic heterocycles such as piperazine, tetrahydropyran, pyran, 1,4-dioxane, thiane, 2H-thiopyran, 4H-thiopyran, 1,3-dithiane, 1,4-dithiane, 1,
• a " C1-4 hydrocarbyl group” refers to a monovalent group formed by removing one hydrogen atom from a hydrocarbon having 1 to 4 carbon atoms. Hydrocarbyl groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and the like.
• the "C 1-4 hydrocarbyl group” is not particularly limited, and examples thereof include a "C 1-4 alkyl group", a "C 2-14 alkenyl group", a "C 2-4 alkynyl group", a "C 3-4 alicyclic group” and the like.
• a "C 1-4 hydrocarbyloxy group” refers to a “C 1-4 hydrocarbyl group” to which an oxygen atom (-O-) is bonded.
• the "C 1-4 hydrocarbyloxy group” is not particularly limited, and examples include “C 1-4 alkoxy groups” such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, and a t-butoxy group; and "C 3-4 alicyclic oxy groups” such as a cyclopropyloxy group and a cyclobutyloxy group.
• the "C 1-4 hydrocarbylcarbonyl group” is not particularly limited, and examples thereof include “C 1-4 alkylcarbonyl groups” such as an acetyl group, a propionyl group, an isopropionyl group, a butyryl group, and an isobutyryl group; and “C 3-4 alicyclic carbonyl groups” such as a cyclopropylcarbonyl group and a cyclobutylcarbonyl group.
• C 1-4 hydrocarbylcarbonyloxy group refers to a "C 1-4 hydrocarbylcarbonyl group” to which an oxygen atom (-O-) is bonded.
• the "C 1-4 hydrocarbylcarbonyloxy group” is not particularly limited, and examples include "C 1-4 alkylcarbonyloxy groups” such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n - butylcarbonyloxy group, an isobutylcarbonyloxy group, and a t-butylcarbonyloxy group; and "C 3-4 alicyclic carbonyloxy groups” such as a cyclopropylcarbonyloxy group and a cyclobutylcarbonyloxy group.
• the "C 1-4 hydrocarbyloxycarbonyl group” is not particularly limited, and examples include "C 1-18 alkoxycarbonyl groups” such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, a sec-butoxycarbonyl group, and a t-butoxycarbonyl group; and "C 3-18 alicyclic oxycarbonyl groups” such as a cyclopropyloxycarbonyl group and a cyclobutyloxycarbonyl group.
• C 1-4 hydrocarbylamino group refers to a group in which one "C 1-4 hydrocarbyl group” is bonded to an amino group.
• the “C 1-4 hydrocarbylamino group” is not particularly limited, and examples include “C 1-4 alkylamino groups” such as methylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, i-butylamino group, sec-butylamino group, and t-butylamino group; and "C 3-4 alicyclic amino groups” such as cyclopropylamino group and cyclobutylamino group.
• di-C 1-4 hydrocarbylamino group refers to a group in which two identical or different "C 1-4 hydrocarbyl groups” are bonded to an amino group.
• the "di-C 1-4 dihydrocarbylamino group” is not particularly limited, and examples thereof include “di-C 1-4 alkylamino groups” such as dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-t-butylamino group, N-ethyl-N-methylamino group, N-methyl-N- n- propylamino group, N-isopropyl-N-methylamino group, N-n-butyl-N-methylamino group, N-isobutyl-N-methylamino group, and N-t-butyl-N-methyla
• the "C 1-4 hydrocarbylaminocarbonyl group” is not particularly limited, and examples include "C 1-4 alkylaminocarbonyl groups” such as a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an i-propylaminocarbonyl group, an n-butylaminocarbonyl group, a sec-butylaminocarbonyl group, and a t-butylaminocarbonyl group; and "C 3-4 alicyclic aminocarbonyl groups” such as a cyclopropylaminocarbonyl group and a cyclobutylaminocarbonyl group.
• the "di-C 1-4 hydrocarbylaminocarbonyl group” is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a diisopropylaminocarbonyl group, a di-n-butylaminocarbonyl group, a diisobutylaminocarbonyl group, a di-t-butylaminocarbonyl group, an N-ethyl-N-methylaminocarbonyl group, an N-methyl-N-n-propylaminocarbonyl group, an N-isopropyl- "di-C 1-4 alkylamino groups" such as an N-methylaminocarbonyl group, an N-n-butyl-N-methylaminocarbonyl group, an N-isobutyl-N-methylaminocarbonyl group, an N-t-butyl
• C 1-4 hydrocarbylcarbonylamino group refers to a group in which an amino group is bonded to a "C 1-4 hydrocarbylcarbonyl group”.
• the "C 1-4 hydrocarbylcarbonylamino group” is not particularly limited, and examples include "C 1-18 alkylcarbonylamino groups” such as a methylcarbonylamino group, an ethylcarbonylamino group, an n-propylcarbonylamino group, an i-propylcarbonylamino group, an n-butylcarbonylamino group, an i-butylcarbonylamino group, a sec-butylcarbonylamino group, and a t-butylcarbonylamino group; and "C 3-4 alicyclic carbonylamino groups” such as a cyclopropylcarbonylamino group and a cyclobutylcarbonylamino group.
• a "C 1-4 hydrocarbylthio group” refers to a “C 1-4 hydrocarbyl group” having a sulfur atom (-S-) bonded to it.
• the "C 1-4 hydrocarbylthio group” is not particularly limited, and examples include “C 1-4 alkylthio groups” such as a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, and a t-butylthio group; and "C 3-18 alicyclic thio groups” such as a cyclopropylthio group and a cyclobutylthio group.
• C 1-4 hydrocarbylsulfinyl group is not particularly limited, and examples thereof include "C 1-4 alkylsulfinyl groups” such as a methylsulfinyl group, an ethylsulfinyl group, an n-propylsulfinyl group, an i-propylsulfinyl group , an n-butylsulfinyl group, and a t-butylsulfinyl group; and "C 3-4 alicyclic sulfinyl groups” such as a cyclopropylsulfinyl group and a cyclobutylsulfinyl group.
• C 1-4 hydrocarbylsulfonyl group refers to a “C 1-4 hydrocarbyl group” having a sulfonyl group (-SO 2 -) bonded to it.
• the "C 1-4 hydrocarbylsulfonyl group” is not particularly limited, and examples include "C 1-4 alkylsulfonyl groups” such as a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonyl group , an n-butylsulfonyl group, and a t-butylsulfonyl group; and "C 3-4 alicyclic sulfonyl groups” such as a cyclopropylsulfonyl group and a cyclobutylsulfonyl group.
• hydroxy group or carboxy group having a protecting group means a hydroxy group (including a phenolic hydroxyl group) or a carboxy group that is protected by an ether-based protecting group, a silyl ether-based protecting group, an acyl-based protecting group, an aminocarbonyl-based protecting group, or the like.
• the ether-based protecting group is not particularly limited, and examples thereof include a methyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a triphenylmethyl group, a p-methoxyphenyldiphenylmethyl group, and a di(p-methoxyphenyl)phenylmethyl group.
• the silyl ether protecting group is not particularly limited, and examples thereof include t-butyldimethylsilyl group (TBS), triisopropylsilyl group (TIPS), trimethylsilyl group (TMS), triethylsilyl group (TES), and t-butyldiphenylsilyl group (TBDPS).
• the acyl protecting group is not particularly limited, and examples thereof include an acetyl group, a pivaloyl group, and a benzoyl group.
• the aminocarbonyl protecting group is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, and an N-phenyl-N-methyl-aminocarbonyl group.
• the treatment liquid according to the present embodiment is characterized in that it contains 20% by mass or more of a first solvent, which is at least one solvent selected from the group consisting of the following (1) to (4). Furthermore, the treatment liquid more preferably contains 20 to 80% by mass of the first solvent, and even more preferably contains 20 to 50% by mass.
• a first solvent which is at least one solvent selected from the group consisting of the following (1) to (4).
• the treatment liquid more preferably contains 20 to 80% by mass of the first solvent, and even more preferably contains 20 to 50% by mass.
• a benzene ring in which one or more hydrogen atoms are substituted with a polar substituent.
• a 5- or 6-membered aromatic heterocycle in which one or more hydrogen atoms may be substituted with a polar substituent.
• a 5- or 6-membered hydrocarbon ring having one or more double bonds in the ring and at least one or more hydrogen atoms substituted with a polar substituent, or having a carbonyl group in the ring and at least one or more hydrogen atoms may be substituted with a polar substituent.
• the "benzene ring having one or more hydrogen atoms substituted with a polar substituent" used in the treatment liquid according to this embodiment is not particularly limited, and any known or commonly used one can be used. Note that, in the benzene ring, it is sufficient that one or more hydrogen atoms are substituted with a polar substituent, and the remaining hydrogen atoms may be substituted with a C 1-4 hydrocarbyl group.
• benzene rings in which one or more hydrogen atoms are replaced by polar substituents include phenol, anisole, 2-phenoxyethanol, o-cresol, m-cresol, p-cresol, 2-aminophenol, 3-aminophenol, 4-aminophenol, catechol, benzoic acid, methyl benzoate, ethyl benzoate, methyl 2-methoxybenzoate, methyl 3-methoxybenzoate, methyl 4-methoxybenzoate, aniline, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, butylphenyl ether, 4-methylsalicylic acid, trans-o-coumaric acid, trans-m-coumaric acid, trans-p-coumaric acid, 1,2-diaminophenyl ether, Methoxybenzene, 1,3-dimethoxybenzene, 1,4-dime
• the solvents used in the treatment solution according to this embodiment are preferably nitrobenzene, benzonitrile, phenol, aniline, anisole, dimethoxybenzene, N-methylaniline, N-ethylaniline, thioanisole, ethylphenylsulfide, benzaldehyde, acetophenone, propiophenone, 2-phenoxyethanol, 2-(benzylthio)ethanol, methyl benzoate, ethyl benzoate, benzyl alcohol, benzylamine, 1-phenylethylamine, and benzyl mercaptan, from the viewpoint that the solvent has planarity in part of the molecule and has asymmetry due to the polar substituent. Nitrobenzene, benzonitrile, phenol, aniline, anisole, thioanisole, benzaldehyde, acetophenone, 2-phenoxyethanol, benzyl alcohol, and benzylamine are even more preferable.
• the "5- or 6-membered aromatic heterocycle in which one or more hydrogen atoms may be substituted with a polar substituent" used in the treatment liquid according to this embodiment is not particularly limited, and any known or commonly used one may be used.
• one or more hydrogen atoms may be substituted with a polar substituent, or one or more hydrogen atoms may be substituted with a C 1-4 hydrocarbyl group.
• Examples of "5-membered aromatic heterocycles in which one or more hydrogen atoms may be substituted with polar substituents" include pyrrole, 3-methylpyrrole, 1-methylpyrrole, 1-ethylpyrrole, 1-aminopyrrole, 1H-pyrrole-2-carbonitrile, pyrrole-2-carbaldehyde, pyrrole-3-carbaldehyde, 2,5-dimethylpyrrole, 2-ethylpyrrole, 2,4-dimethylpyrrole, 1-methylpyrrole-2-carbonitrile, 2-acetylpyrrole, and 2-acetyl-1-methylpyrrole.
• examples of "6-membered aromatic heterocycles in which one or more hydrogen atoms may be substituted with a polar substituent” include pyridine, 2-pyridinemethanol, 3-pyridinemethanol, 2-(1-hydroxyethyl)pyridine, 2-methoxypyridine, 2-ethoxypyridine, 3-methoxypyridine, 3-ethoxypyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetylpyridine, 3-acetylpyridine, 4-acetylpyridine, 2-cyanopyridine, 2-cyano-4-nitropyridine, 3,4-diaminopyridine, 4-dimethylaminopyridine, isonicotinamide, methyl pyridine-4-carboxylate, pyridine-4-carboxylic acid, nicotinamide, methyl pyridine-4-carboxylate ...
• amide nicotinic acid, 2-aminonicotinic acid, 6-aminonicotinic acid, pyridine-2-carboxylic acid, 3-pyridylacetic acid, 2,3-dihydroxypyridine, 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine, 3-(2-aminoethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 2-amino-5-cyanopyridine, 4-acetamidopyridine, 2-acetamidopyridine, 2-aminopyrimidine, 5-aminopyrimidine, 2-cyanopyrimidine, 4-hydroxy-6-methylpyrimidine, 3-methoxypyrimidine, 4-methoxypyrimidine, pyridazine-4-carboxylic acid, 1,3,5-triazine, 2,4-diamino-1,3,5-triazine, etc.
• the solvents used in the treatment liquid according to this embodiment are those that have planarity in part of their molecules and have polarity, and among these solvents, the following are particularly preferred: 1-aminopyrrole, 1H-pyrrole-2-carbonitrile, pyrrole-2-carbaldehyde, pyrrole-3-carbaldehyde, 2-acetylpyrrole, 2-furonitrile, furfural, 3-furaldehyde, furfurylamine, furfuryl alcohol, 3-furanmethanol, 2-acetylfuran, 5-acetoxymethylfurfural, furfuryl mercaptan, 2-furancarboxylic acid, 2-furan methyl carboxylate, 2-furan ethyl carboxylate, furfuryl methyl sulfide, pyridine, 2-pyridinemethanol, 3-pyridinemethanol, 2-(1-hydroxyethyl)pyridine, 2-methyl-2-pyridinemethanol ...
• the "five- or six-membered hydrocarbon ring having one or more double bonds in the ring and at least one or more hydrogen atoms optionally substituted with a polar substituent, or having a carbonyl group in the ring and at least one or more hydrogen atoms optionally substituted with a polar substituent" used in the treatment liquid according to this embodiment is not particularly limited, and any known or commonly used one can be used.
• one or more hydrogen atoms may be substituted with a C 1-4 hydrocarbyl group.
• Examples of "a five- or six-membered hydrocarbon ring having one or more double bonds in the ring and at least one or more hydrogen atoms being replaced by a polar substituent" include 1-cyclopentenecarboxylic acid, 1-acetyl-1-cyclopentene, 1-methoxycyclopentene, 3-cyclopentene-1-methanol, 3-methoxy-2-cyclopenten-1-one, 1-acetyl-1-cyclopenten-3-one, 1-cyclohexen-1-ol, 3-methoxycyclohexene, 3 -Cyclohexene-1-methanol, 1-cyclohexene-1-carboxylic acid, 3-cyclohexene-1-carboxylic acid, 4-methyl-3-cyclohexene-1-carboxylic acid, 3-cyclohexene-1-methyl carboxylate, cis-4-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1-carboxaldehyde, 1-
• Examples of the "5- or 6-membered hydrocarbon ring having a carbonyl group in the ring and at least one hydrogen atom of which may be substituted with a polar substituent" include cyclopentanone, cyclohexanone,
• Examples of the cyclopentene-1-one include 2-cyclopentene-1-one, 1,3-cyclopentanedione, 3-hydroxy-3-methyl-2-cyclopentenone, 2-acetylcyclopentanone, 2-oxocyclopentanecarboxylate ethyl, 2-cyclohexene-1-one, 3-methyl-2-cyclohexene-1-one, 3-aminocyclohexanone, 2-methoxycyclohexanone, and 4-acetamidocyclohexanone.
• the solvents used in the treatment solution according to this embodiment have a double bond or carbonyl group that induces planarity in part of the molecule, and are polar, and therefore, among these solvents, 1-acetyl-1-cyclopentene, 3-cyclopentene-1-methanol, 1-cyclohexen-1-ol, 3-methoxycyclohexene, 3-cyclohexene-1-methanol, 3-cyclohexene-1-methylcarboxylate, 1-acetyl-1-cyclohexene, 4-acetyl-1-cyclohexene, cyclopentanone, 2-cyclohexen-1-one, cyclohexanone, 2-acetylcyclopentanone, 2-methoxycyclohexanone, 4-acetamidocyclohexanone is preferred, 1-acetyl-1-cyclopentene, 1-cyclohexen-1-ol, 3-methoxycyclohexene, methyl 3-cyclohexene-1-
• the "5- or 6-membered non-aromatic heterocycle in which at least one hydrogen atom is substituted with a polar substituent, or which has a total of two or more heteroatoms or carbonyl groups in the ring and in which at least one hydrogen atom may be substituted with a polar substituent" used in the treatment liquid according to this embodiment is not particularly limited, and any known or commonly used one can be used.
• one or more hydrogen atoms may be substituted with a C 1-4 hydrocarbyl group.
• Examples of "5- or 6-membered non-aromatic heterocycles in which at least one hydrogen atom is substituted with a polar substituent” include 3-aminopyrrolidine, 3-pyrrolidinol, 2-(methoxymethyl)pyrrolidine, prolinol, proline, 2,5-dimethoxytetrahydrofuran, 1,4-anhydroerythritol, 2-aminomethyl-1-methylpyrrolidine, 2-aminomethyl-2-ethylpyrrolidine, tetrahydro-2H-pyran-4-amine, tetrahydro-4-pyranol, 4-aminomethyltetrahydropyran, penta-O-acetyl- ⁇ -D -glucopyranose, galactose, 4-aminopiperidine, 2-piperidinemethanol, 3-piperidinemethanol, 1-methyl-3-piperidinemethanol, 3-piperidinecarboxylic acid, ethyl 2-piperidinecarboxylate,
• Examples of "5- or 6-membered non-aromatic heterocycles having two or more heteroatoms or carbonyl groups in the ring, and at least one or more hydrogen atoms may be substituted with a polar substituent" include, for example, tetrahydro-4H-pyran-4-one, ⁇ -valerolactone, glutaric anhydride, ⁇ -hexanolactone, 1,4-dioxane, 1,4-dioxane 2,3-diol, 2-pyrrolidone, 5-methyl-2-pyrrolidone, 1-methyl-2-pyrrolidone, 2-piperidone, 1-acetylacetonin ...
• the solvents used in the treatment solution according to this embodiment are polar or have a carbonyl group in the ring, which induces planarity.
• the treatment liquid according to this embodiment may contain 1 to 80 mass % of one or more second solvents different from the first solvent.
• the second solvent water, an alcohol-based solvent, an amide-based solvent, an ester-based solvent, an ether-based solvent, a ketone-based solvent, a hydrocarbon-based solvent, or the like can be used.
• the alcohol solvent include alcohols such as MeOH, EtOH, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, and n-heptyl alcohol; glycols such as ethylene glycol, diethylene glycol, and triethylene glycol; and glycol ethers having a hydroxyl group such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobuty
• amide solvent examples include dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone.
• ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 2-hydroxyisobutyrate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate,
• ether solvent examples include propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 1,4-dioxane, tetrahydrofuran, and anisole.
• ketone solvent examples include acetone, 1-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cycloheptanone, cyclohexanone, methyl ethyl ketone, acetylacetone, and ⁇ -butyrolactone.
• hydrocarbon solvent examples include aliphatic hydrocarbon solvents such as n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, and methylethylbenzene. These solvents may be used alone or in combination of two or more.
• the second solvent is preferably one or more solvents selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and water.
• the above-mentioned treatment liquid can be suitably used as a developer for developing the metal compound-containing film after the exposure step, and as a rinse liquid for rinsing the developed metal compound-containing film.
• the treatment liquid according to this embodiment has a difference in solubility between the exposed and unexposed parts of the metal compound-containing film, and can provide a contrast between the exposed and unexposed parts.
• the treatment solution can be suitably used as a negative developer for developing a metal compound-containing film after exposure to an ArF excimer laser (wavelength 193 nm), a KrF excimer laser (248 nm), an F2 excimer laser (wavelength 157 nm), EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, etc.
• an ArF excimer laser wavelength 193 nm
• a KrF excimer laser (248 nm
• an F2 excimer laser wavelength 157 nm
• EUV extreme ultraviolet
• VUV vacuum ultraviolet
• EB electrotron beam
• X-ray X-ray
• the pattern forming method according to this embodiment includes a step of treating the exposed metal compound-containing film with a treatment liquid.
• the method of developing the metal compound-containing film using the treatment liquid as a developer is not particularly limited, and any known, commonly used method can be used.
• methods of development using the treatment liquid include a method of immersing a substrate having a metal compound-containing film after exposure in the treatment liquid for a certain period of time (dip method), a method of spraying the treatment liquid on the surface of the metal compound-containing film after exposure (spray method), and a method of discharging the treatment liquid at a constant speed from a discharge nozzle toward the surface of the metal compound-containing film after exposure on a substrate rotating at a constant speed (dynamic dispense method).
• the method of using the treatment liquid as a rinsing liquid to wash the metal compound-containing film pattern after development is not particularly limited, and any known, commonly used method can be used.
• methods for rinsing using the treatment liquid include a method of immersing a substrate having a metal compound-containing film pattern in the treatment liquid for a certain period of time (dip method), a method of spraying the treatment liquid onto the surface of the metal compound-containing film pattern (spray method), and a method of ejecting the treatment liquid at a constant speed from an ejection nozzle toward the surface of the metal compound-containing film pattern on a substrate rotating at a constant speed (spin coating method).
• the metal compound-containing film treatment solution according to the present embodiment is characterized in that it contains 20% by mass or more of a first solvent which is one or more selected from the group consisting of: (1) a benzene ring in which one or more hydrogen atoms are substituted with a polar substituent; (2) a 5- or 6-membered aromatic heterocycle in which one or more hydrogen atoms may be substituted with a polar substituent; (3) a 5- or 6-membered hydrocarbon ring having one or more double bonds in the ring and at least one or more hydrogen atoms being substituted with a polar substituent, or having a carbonyl group in the ring and at least one or more hydrogen atoms being substituted with a polar substituent; and (4) a 5- or 6-membered non-aromatic heterocycle in which at least one hydrogen atom is substituted with a polar substituent, or having a total of two or more heteroatoms or carbonyl groups in the ring and at least one
• a first solvent which is one or
• the treatment solution for metal compound-containing films may further contain 1 to 80 mass % or more of one or more second solvents different from the first solvent.
• the second solvent is preferably one or more solvents selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, and water, which are different from the first solvent.
• the metal compound-containing film treatment liquid according to this embodiment is capable of forming a good pattern even when the metal compound-containing film contains polyoxometalate as the metal compound, and can be suitably used as a polyoxometalate-containing film treatment liquid.
• test metal compound-containing film-forming composition F Hexakis(bis(2-trifluoromethylphenyl)phenylsulfonium)metatungstate (metal compound M) as a metal compound, dimethylformamide (DMF) and ethyl lactate (EL) as solvents were blended so that the content of each component was the amount shown in Table 1 (unit: parts by mass), and mixed with a stirrer to prepare a test metal compound-containing film-forming composition F.
• Metal compound M was synthesized by the following method and used to prepare metal compound-containing film-forming composition F for testing. 6.68 g of bis(2-trifluoromethylphenyl)phenylsulfonium chloride was dissolved in 99.36 g of pure water, and 6.88 g of ammonium metatungstate (ammonium metatungstate hydrate ((NH 4 ) 6 [H 2 W 12 O 40 ].xH 2 O)) was added, and the reaction solution was stirred at room temperature for 30 minutes. The reaction solution was filtered, and the obtained powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was dissolved in 100 g of dimethylformamide, and then 335 g of methanol was added and crystallized at room temperature to obtain metal compound M.
• ammonium metatungstate ammonium metatungstate hydrate ((NH 4 ) 6 [H 2 W 12 O 40 ].xH 2 O)
• test membranes Preparation of test membranes ⁇ Film formation process> A test metal compound-containing film-forming composition F was applied using a spinner onto an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HDMS), and post-applied bake (PAB) treatment was performed on a hot plate at a temperature of 200° C. for 60 seconds, followed by drying to form a test metal compound-containing film having a film thickness of 50 nm. The average thickness of the formed metal compound-containing film was measured using a film thickness measuring device ("M-2000D" manufactured by J.A. Woollam Co., Ltd.).
• M-2000D manufactured by J.A. Woollam Co., Ltd.
• test film was developed for 60 seconds at 23° C. using treatment solutions A-1 to A-9 (benzene ring or aromatic heterocycle) and B-1 to B-10 (non-aromatic heterocycle, aromatic heterocycle, or hydrocarbon ring) shown in Tables 2 and 3 below, and then rinsed for 15 seconds at 23° C. using 2-propanol. Thereafter, the change in film thickness between the exposed and unexposed areas was measured using a film thickness measuring device.
• A-1 to A-9 benzene ring or aromatic heterocycle
• B-1 to B-10 non-aromatic heterocycle, aromatic heterocycle, or hydrocarbon ring
• the planarity of the cyclic compound is improved by having a double bond in the hydrocarbon ring or a carbonyl group, and when a double bond is present in the hydrocarbon ring, and a solvent having a polar substituent such as an aldehyde group is used as the processing solution as in processing solution B-7, the evaluation of the amount of film loss in the unexposed areas of the test film was all rated as A, indicating that good results were obtained.
• test film was developed for 60 seconds using treatment liquids C-1 to C-7 (combinations of benzyl alcohol and PGMEA) shown in Table 4 below, treatment liquids D-1 to D-7 (combinations of anisole and PGMEA) shown in Table 5 below, and treatment liquids E-1 to E-7 (combinations of acetophenone and PGMEA) shown in Table 6 below, and then rinsed for 15 seconds using 2-propanol. Thereafter, the change in film thickness between the exposed and unexposed areas was measured using a film thickness measuring device. Tables 4 to 6 show the (mass) ratios of solvents 1 and 2 in each treatment liquid.
• test film was developed for 60 seconds using treatment solutions F-1 to F-19 (combinations of benzyl alcohol and the second solvent) shown in Table 7 below, treatment solutions G-1 to G-6 (combinations of anisole and the second solvent) shown in Table 8 below, and treatment solutions G-7 to G-12 (combinations of acetophenone and the second solvent) shown in Table 8 below, and then rinsed for 15 seconds using 2-propanol. Thereafter, the change in film thickness between the exposed and unexposed areas was measured using a film thickness measuring device. Tables 7 and 8 show the (mass) ratios of solvents 1 and 2 in each treatment liquid, respectively.
• the test membrane was evaluated for the amount of film loss in the unexposed area and for selectivity according to the same criteria as above. The results are shown in Tables 7 and 8.

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