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
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
• • 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
  • G03F7/004—Photosensitive materials
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
  • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
• • 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
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive 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
• • 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
  • G03F7/16—Coating processes; 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
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • 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
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
• • 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
• • 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
  • G03F7/325—Non-aqueous compositions
• • 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
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • 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
  • G03F7/40—Treatment after imagewise removal, e.g. baking
  • G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
• • 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
  • G03F7/70—Microphotolithographic exposure; Apparatus therefor
  • G03F7/70008—Production of exposure light, i.e. light sources
  • G03F7/70033—Production of exposure light, i.e. light sources by plasma extreme ultraviolet [EUV] sources

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 conducted extensive research to solve the above problems, and discovered that after exposing a metal compound-containing film to light, the unexposed areas of the metal compound-containing film can be selectively reduced and a pattern can be formed by using a treatment solution containing an organic solvent, the organic solvent containing one or more first solvents that satisfy (1) ClogP ⁇ 0.7 and (2) ⁇ H+ ⁇ P ⁇ 16, and the content of the first solvent is 30% by mass or more relative to 100% by mass of the organic solvent, and thus completing the present invention.
• 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 contains an organic solvent, the organic solvent comprises one or more first solvents having a ClogP ⁇ 0.7 and a ⁇ H+ ⁇ P ⁇ 16;
• the content of the first solvent is 30% by mass or more relative to 100% by mass of the organic solvent.
• 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 contains an organic solvent, the organic solvent comprises one or more first solvents having a ClogP ⁇ 0.7 and a ⁇ H+ ⁇ P ⁇ 16; The content of the first solvent is 30% by mass or more relative to 100% by mass of the organic solvent. Pattern formation method.
• the organic solvent further contains one or more second solvents different from the first solvent, The content of the second solvent is 1 to 70% by mass with respect to 100% by mass of the organic solvent.
• the second solvent is different from the first solvent and is one or more organic solvents selected from the group consisting of alcohol solvents containing 3 or more carbon atoms, ester solvents containing 3 or less oxygen atoms, and ketone solvents containing 2 or less oxygen atoms.
• the second solvent is one or more solvents in which ClogP>0.7 and ⁇ H+ ⁇ P ⁇ 25, or ClogP ⁇ 0.35 and ⁇ H+ ⁇ P ⁇ 16; The pattern forming method according to [3].
• the second solvent is one or more solvents selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, butyl acetate, 3-methoxy-3-methyl-1-butanol, 4-methyl-2-pentanol (MIBC), methyl isobutyl ketone (MIBK), benzyl alcohol, t-butyl alcohol, octanol, hexane, decane, and diethylene glycol monobutyl ether (BDG);
• PMEA propylene glycol monomethyl ether acetate
• MIBC methyl isobutyl ketone
• MIBK methyl isobutyl ketone
• benzyl alcohol t-butyl alcohol
• octanol hexane
• decane and diethylene glycol monobutyl ether
• BDG diethylene glycol monobutyl ether
• a treatment liquid for a metal compound-containing film comprising: The treatment liquid contains an organic solvent, the organic solvent comprises one or more first solvents having a ClogP ⁇ 0.7 and a ⁇ H+ ⁇ P ⁇ 16; The content of the first solvent is 30% by mass or more relative to 100% by mass of the organic solvent. Treatment solution for metal compound-containing films.
• the organic solvent further contains one or more second solvents different from the first solvent,
• the second solvent is different from the first solvent and is one or more organic solvents selected from the group consisting of alcohol solvents containing 3 or more carbon atoms, ester solvents containing 3 or less oxygen atoms, and ketone solvents containing no more than 2 oxygen atoms.
• the second solvent is one or more solvents in which ClogP>0.7 and ⁇ H+ ⁇ P ⁇ 25, or ClogP ⁇ 0.35 and ⁇ H+ ⁇ P ⁇ 16.
• the second solvent is one or more solvents selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, butyl acetate, 3-methoxy-3-methyl-1-butanol, 4-methyl-2-pentanol (MIBC), methyl isobutyl ketone (MIBK), benzyl alcohol, t-butyl alcohol, octanol, hexane, decane, and diethylene glycol monobutyl ether (BDG);
• the treatment solution for a metal compound-containing film according to [15] further comprising water.
• 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 an organic solvent, the organic solvent contains one or more first solvents that satisfy the following conditions (1) and (2), and the content of the first solvent is 30% by mass or more relative to 100% by mass of the organic solvent.
• the treatment liquid contains an organic solvent
• the organic solvent contains one or more first solvents that satisfy the following conditions (1) and (2)
• the content of the first solvent is 30% by mass or more relative to 100% by mass of the organic solvent.
• 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
• hydroxy group or carboxy group having a protecting group refers to a hydroxy group (including a phenolic hydroxyl group) or a carboxy group which 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).
• TBS t-butyldimethylsilyl group
• TIPS triisopropylsilyl group
• TMS trimethylsilyl group
• TES triethylsilyl group
• TDPS t-butyldiphenylsilyl group
• 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.
• 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 mass%, more preferably 1 to 20 mass%, and even more preferably 1 to 10 mass%, assuming that the metal compound-containing film-forming composition is 100 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.
• the organic solvent 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,
• the solvent include esters such as n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lac
• organic solvents may be used alone or in combination of two or more.
• the organic solvent contained in the metal compound-containing film-forming composition according to this embodiment it is preferable to use propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ⁇ -butyrolactone (GBL), methanol, water, or a combination thereof.
• PGME propylene glycol monomethyl ether
• PGMEA propylene glycol monomethyl ether acetate
• EL ethyl lactate
• GBL ⁇ -butyrolactone
• 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.
• the treatment liquid according to the present embodiment contains an organic solvent.
• the content of the organic solvent contained in the treatment liquid is not particularly limited and can be appropriately set depending on the type of organic solvent, the type of the target metal compound-containing film, and the like.
• the content of the organic solvent contained in the treatment liquid is preferably 25 to 100 mass %, more preferably 30 to 100 mass %, and even more preferably 30 to 90 mass %, relative to 100 mass % of the treatment liquid.
• the organic solvent contains one or more first solvents that satisfy the following conditions (1) and (2).
• the ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water.
• the method and software used to calculate the ClogP value may be any known or commonly used method and software.
• the ClogP value calculated by DataWarrior V5.5.0 (www.openmolecules.org) is used.
• the Hansen solubility parameters are expressed in three-dimensional space by dividing the solubility of a substance into three components, the dispersion term ⁇ D, the polar term ⁇ P, and the hydrogen bond term ⁇ H, where the dispersion term ⁇ D indicates the effect of dispersion forces, the polar term ⁇ P indicates the effect of dipole-dipole forces, and the hydrogen bond term ⁇ H indicates the effect of hydrogen bonds.
• the Hansen solubility parameters can be calculated using known and commonly used methods and software. In this specification, the estimated values of ⁇ H and ⁇ P calculated using Hansen Solubility Parameters in Practice (HSPiP) 5th edition 5.4.02 are used.
• the organic solvent contained in the treatment liquid according to this embodiment includes one or more first solvents that satisfy (1) ClogP ⁇ 0.7 and (2) ⁇ H+ ⁇ P ⁇ 16.
• the content of the first solvent contained in the organic solvent is preferably 30% by mass or more, more preferably 30 to 90% by mass, and even more preferably 40 to 80% by mass, relative to 100% by mass of the organic solvent.
• Examples of the first solvent that satisfies the above conditions (1) and (2) include, but are not limited to, DMF, MeOH, EtOH, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, 3-methoxy-1-butanol, PE or PGME, acetylacetone, hydroxyacetone, 4-hydroxy-2-butanone, diacetone alcohol, methyl 2-hydroxyisobutyrate, ethyl lactate (EL), ⁇ -butyrolactone, acetonitrile, dimethylacetamide, dimethylsulfoxide, and ethylene glycol. These solvents may be used alone or in combination of two or more.
• the organic solvent contained in the treatment liquid according to the present embodiment may contain one or more second solvents different from the first solvent.
• the content of the second solvent contained in the organic solvent is not particularly limited, and from the viewpoint of selectively reducing the film in the unexposed area, the second solvent is preferably contained in an amount of 1 to 70 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 60 mass %, relative to 100 mass % of the organic solvent.
• 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 other than the organic solvent contained in the first solvent can be used.
• the alcohol solvent examples include alcohols such as tert-butyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octanol, and 4-methyl-2-pentanol (MIBC); glycols such as triethylene glycol; and glycol ethers having a hydroxyl group such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.
• alcohols such as tert-butyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octanol, and 4-methyl-2-pentanol (MIBC)
• glycols such as triethylene glycol
• amide solvent is N-methyl-2-pyrrolidone.
• ester-based solvents include butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, butyl lactate, dibutyl carbonate, propylene glycol monomethyl ether acetate (PGMEA), 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, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, and 4-methoxybutyl acetate.
• ether solvent examples include propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and anisole.
• ketone solvents include 1-hexanone, 2-hexanone, 1-heptanone, 2-heptanone, diisobutyl ketone, cyclohexanone, cycloheptanone, and methyl isobutyl ketone (MIBK).
• hydrocarbon solvent examples include butane, pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane. These solvents may be used alone or in combination of two or more.
• the alcohol-based solvent used as the second solvent is preferably an alcohol-based solvent containing 3 or more carbon atoms, such as tert-butyl alcohol, n-hexyl alcohol, n-heptyl alcohol, octanol, 4-methyl-2-pentanol (MIBC), and more preferably an alcohol-based solvent containing 3 to 12 carbon atoms.
• an alcohol-based solvent containing 3 or more carbon atoms such as tert-butyl alcohol, n-hexyl alcohol, n-heptyl alcohol, octanol, 4-methyl-2-pentanol (MIBC), and more preferably an alcohol-based solvent containing 3 to 12 carbon atoms.
• the ester solvent used as the second solvent is preferably an ester solvent containing three or less oxygen atoms, such as butyl acetate, butyl lactate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, or 4-methoxybutyl acetate.
• PMEA propylene glycol monomethyl ether acetate
• ethylene glycol monoethyl ether acetate ethylene glycol monopropyl ether acetate
• 2-methoxybutyl acetate 2-methoxybutyl acetate
• 3-methoxybutyl acetate 2-methoxybutyl acetate
• 4-methoxybutyl acetate 4-methoxybutyl acetate.
• the ketone solvent used as the second solvent is preferably a ketone solvent that does not contain two or more oxygen atoms, such as 1-hexanone, 2-hexanone, 1-heptanone, 2-heptanone, diisobutyl ketone, cyclohexanone, cycloheptanone, methyl isobutyl ketone (MIBK), etc.
• the second solvent one or more organic solvents in which (3) ClogP>0.7 and (4) ⁇ H+ ⁇ P ⁇ 25, or (5) ClogP ⁇ 0.35 and (6) ⁇ H+ ⁇ P ⁇ 16.
• Examples of the second solvent satisfying the above (3) and (4), or the above (5) and (6) include, but are not limited to, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, butyl acetate, 3-methoxy-3-methyl-1-butanol, 4-methyl-2-pentanol (MIBC), methyl isobutyl ketone (MIBK), benzyl alcohol, t-butyl alcohol, octanol, hexane, decane, and diethylene glycol monobutyl ether (BDG). These solvents may be used alone or in combination of two or more.
• PMEA propylene glycol monomethyl ether acetate
• MIBC methyl isobutyl ketone
• MIBK methyl isobutyl ketone
• BDG diethylene glycol monobutyl ether
• the second solvent is preferably one or more organic solvents different from the first solvent and selected from the group consisting of alcohol solvents, ester solvents, and ketone solvents, and more preferably one or more solvents different from the first solvent and selected from the group consisting of alcohol solvents containing 3 or more carbon atoms, ester solvents containing 3 or less oxygen atoms, and ketone solvents containing no more than 2 oxygen atoms, and in addition, (3) ClogP>0.7, and (4) ⁇ H+ ⁇ P ⁇ 25, or (5) ClogP ⁇ 0 .35, and (6) one or more solvents in which ⁇ H+ ⁇ P ⁇ 16 are more preferable, and one or more organic solvents selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, butyl acetate, 3-methoxy-3-methyl-1-butanol, 4-methyl-2-pentanol (MIBC), methyl isobutyl ketone (MIB
• the treatment liquid according to the present embodiment may further contain water.
• water itself is a poor solvent for the metal compound-containing film, by including water in the treatment liquid, the performance of the formed pattern can be improved compared to the case where only an organic solvent is used as the treatment liquid.
• the amount of water contained in the treatment liquid is not particularly limited, but if the treatment liquid is taken as 100% by mass, it is preferable that the treatment liquid contains 1 to 75% by mass of water, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass.
• 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 liquid according to the present embodiment contains an organic solvent.
• the content of the organic solvent contained in the metal compound-containing film treatment liquid is not particularly limited, and can be appropriately set depending on the type of organic solvent, the type of the target metal compound-containing film, and the like.
• the content of the organic solvent contained in the metal compound-containing film treatment liquid is preferably 25 to 100 mass %, more preferably 30 to 100 mass %, and even more preferably 30 to 90 mass %, based on 100 mass % of the metal compound-containing film treatment liquid.
• the metal compound-containing film treatment solution according to this embodiment is characterized in that it contains at least one first solvent, with ClogP ⁇ 0.7 and ⁇ H+ ⁇ P ⁇ 16, in an organic solvent in an amount of at least 30% by mass, assuming the organic solvent to be 100% by mass.
• the organic solvent in the metal compound-containing film treatment solution according to another embodiment may further contain one or more second solvents different from the first solvent, in an amount of 1 to 70% by mass relative to 100% by mass of the organic solvent.
• the content of the second solvent contained in the organic solvent is preferably 1 to 70% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass relative to 100% by mass of the organic solvent.
• the second solvent is preferably one or more solvents different from the first solvent and selected from the group consisting of alcohol solvents, ester solvents, and ketone solvents, and more preferably one or more solvents different from the first solvent and selected from the group consisting of alcohol solvents containing 3 or more carbon atoms, ester solvents containing 3 or less oxygen atoms, and ketone solvents containing no more than 2 oxygen atoms, and in addition, (3) ClogP>0.7, and (4) ⁇ H+ ⁇ P ⁇ 25, or (5) ClogP ⁇ 0.3.
• one or more solvents in which ⁇ H+ ⁇ P ⁇ 16 are more preferable one or more solvents in which ⁇ H+ ⁇ P ⁇ 16 are more preferable, and one or more solvents selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, butyl acetate, 3-methoxy-3-methyl-1-butanol, 4-methyl-2-pentanol (MIBC), methyl isobutyl ketone (MIBK), benzyl alcohol, t-butyl alcohol, octanol, hexane, decane, and diethylene glycol monobutyl ether (BDG) are even more preferable.
• PMEA propylene glycol monomethyl ether acetate
• MIBC methyl isobutyl ketone
• MIBK methyl isobutyl ketone
• BDG diethylene glycol monobutyl ether
• the metal compound-containing film treatment liquid may contain water in addition to the organic solvent.
• the water content in the metal compound-containing film treatment liquid is preferably 1 to 75 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 60 mass %, relative to 100 mass % of the metal compound-containing film treatment liquid.
• 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-24 shown in Table 2 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.
• test film was developed for 60 seconds using treatment solutions B-1 to B-13 containing the first and second solvents shown in Table 3 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. Table 3 shows the (mass) ratios of solvents 1 and 2 in each treatment liquid.
• Table 4 shows the (mass) ratios of solvents 1 and 2 in each treatment liquid.
• 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 Table 4.

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