TW201838972A - 光阻材料及圖案形成方法 - Google Patents
光阻材料及圖案形成方法 Download PDFInfo
- Publication number
- TW201838972A TW201838972A TW107109207A TW107109207A TW201838972A TW 201838972 A TW201838972 A TW 201838972A TW 107109207 A TW107109207 A TW 107109207A TW 107109207 A TW107109207 A TW 107109207A TW 201838972 A TW201838972 A TW 201838972A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- carbon atoms
- branched
- atom
- linear
- Prior art date
Links
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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/04—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
- C07C309/15—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton the nitrogen atom of at least one of the amino groups being part of any of the groups, X being a hetero atom, Y being any atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
- C07C309/31—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups by alkyl groups containing at least three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/32—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings containing at least two non-condensed six-membered aromatic rings in the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/39—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing halogen atoms bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/46—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/48—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/51—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/52—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by doubly-bound oxygen atoms
- C07C309/53—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by doubly-bound oxygen atoms the carbon skeleton containing carbon atoms of quinone rings
- C07C309/54—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by doubly-bound oxygen atoms the carbon skeleton containing carbon atoms of quinone rings at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
- C07C309/56—Y being a hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/63—Halogen-containing esters of saturated acids
- C07C69/635—Halogen-containing esters of saturated acids containing rings in the acid moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—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
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
-
- 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
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
-
- 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
- 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
- G03F7/20—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
- G03F7/2006—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 using coherent light; using polarised 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2037—Exposure with X-ray radiation or corpuscular radiation, through a mask with a pattern opaque to that radiation
-
- 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
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
-
- 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
-
- 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
- G03F7/322—Aqueous alkaline 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
- G03F7/327—Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts
-
- 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
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本發明之課題係提供無論在正型光阻材料或負型光阻材料中均為高感度,且LWR、CDU小的光阻材料,以及使用該光阻材料的圖案形成方法。解決該課題之手段為一種光阻材料包含:基礎聚合物,以及含有下式(A-1)表示之鋶鹽或下式(A-2)表示之錪鹽之酸產生劑。
Description
本發明關於光阻材料及圖案形成方法。
隨著LSI之高積體化與高速化,圖案規則之微細化亦急速進展。尤其是快閃記憶體市場的擴大與記憶容量的增加引領著微細化。就最尖端的微細化技術而言,利用ArF微影所為之65nm節點的器件之量產已在實施中,且次世代之利用ArF浸潤式微影所為之45nm節點之量產準備也在進行中。就次世代之32nm節點而言,候選有:組合了折射率比水高的液體、高折射率透鏡、及高折射率光阻材料之利用超高NA透鏡所為之浸潤式微影、波長13.5nm之極紫外線(EUV)微影、ArF微影之雙重曝光(雙圖案微影)等,且正在進行探討。
由於微細化的進展,已趨近於光之繞射極限,連帶造成光的對比度降低。因光的對比度降低,導致在正型光阻膜發生孔洞圖案、溝圖案的解析度、或焦距寬容度的降低。
伴隨圖案之微細化,線圖案之邊緣粗糙度(LWR)及孔洞圖案之尺寸均勻性(CDU)被視為問題。有人指出會有基礎聚合物、酸產生劑的分佈不均、或凝聚的影響、或酸擴散的影響。此外,LWR隨著光阻膜的薄膜化而有變大的傾向,且隨著微細化進展之薄膜化所導致的LWR之劣化已成為嚴重的問題。
在EUV光阻中,必須同時達成高感度化、高解析度化及低LWR化。雖然酸擴散距離縮短的話LWR即會減小,但會造成低感度化。例如,藉由將曝光後烘烤(PEB)溫度降低,LWR會縮小,但會造成低感度化。增加淬滅劑的添加量也可降低LWR,但會造成低感度化。需要破壞感度與LWR的權衡關係。
[發明所欲解決之課題]
期望開發出在將酸作為觸媒之化學增幅光阻中,為高感度且能使LWR、孔洞圖案之CDU降低的酸產生劑。
本發明係鑑於前述情事而成,目的為提供:無論在正型光阻材料或負型光阻材料中均為高感度,且LWR、CDU小的光阻材料,以及使用該光阻材料的圖案形成方法。 [解決課題之手段]
本發明人們為了達成前述目的而反復深入探討後之結果發現:藉由使用特定之經和碘化苯甲酸鍵結的氟苯磺酸之鋶鹽或錪鹽作為酸產生劑,可獲得LWR及CDU小、對比度高且解析度優良、製程寬容度大的光阻材料,乃至完成本發明。
亦即,本發明係提供下述光阻材料及圖案形成方法。 1. 一種光阻材料,包含:基礎聚合物,及含有下式(A-1)表示之鋶鹽或下式(A-2)表示之錪鹽之酸產生劑。 [化1]式中,R1
為羥基、羧基、氟原子、氯原子、溴原子或胺基、或也可含有氟原子、氯原子、溴原子、羥基、胺基或烷氧基之直鏈狀或分支狀或環狀之碳數1~20之烷基、碳數1~20之烷氧基、碳數2~20之烷氧基羰基或碳數2~20之醯氧基、或-NR9
-C(=O)-R10
或-NR9
-C(=O)-O-R10
,R9
為氫原子,或直鏈狀或分支狀或環狀之碳數1~6之烷基,R10
為直鏈狀或分支狀或環狀之碳數1~16之烷基、直鏈狀或分支狀或環狀之碳數2~16之烯基、或碳數6~12之芳基,且也可含有鹵素原子、羥基、烷氧基、醯基或醯氧基;R2
為單鍵、或也可含有氧原子、硫原子或氮原子之碳數1~20之2價連結基;Rf
為氟原子或三氟甲基;R3
、R4
及R5
各自獨立地為氟原子、氯原子、溴原子、碘原子、直鏈狀或分支狀或環狀之碳數1~12之烷基、直鏈狀或分支狀或環狀之碳數2~12之烯基、碳數6~20之芳基、或碳數7~12之芳烷基或芳氧基烷基,且這些基的氫原子之一部分或全部也可取代為羥基、羧基、鹵素原子、側氧基、氰基、醯胺基、硝基、磺內酯基、碸基或含有鋶鹽之基,這些基的碳原子之一部分也可取代為醚基、酯基、羰基、碳酸酯基或磺酸酯基;又,也可R3
與R4
鍵結並和它們所鍵結的硫原子一起形成環;R6
及R7
為碳數6~10之芳基、碳數2~6之烯基、碳數2~6之炔基或三氟甲基,且這些基的氫原子之一部分或全部也可取代為鹵素原子、三氟甲基、直鏈狀或分支狀或環狀之碳數1~10之烷基或烷氧基、羥基、羧基、烷氧基羰基、硝基或氰基;m為1~5之整數;n為0~3之整數;p為1~4之整數。 2. 如1之光阻材料,更含有淬滅劑。 3. 如1或2之光阻材料,更含有有機溶劑。 4. 如1~3中任一項之光阻材料,其中,前述基礎聚合物包含下式(a1)表示之重複單元或下式(a2)表示之重複單元。 [化2]式中,RA
各自獨立地為氫原子或甲基;X1
為單鍵、伸苯基或伸萘基、或含有選自於酯基及內酯環中之至少1者之碳數1~12之連結基;X2
為單鍵或酯基;R11
及R12
為酸不穩定基;R13
為氟原子、三氟甲基、氰基、直鏈狀或分支狀或環狀之碳數1~6之烷基或烷氧基、或直鏈狀或分支狀或環狀之碳數2~7之醯基、醯氧基或烷氧基羰基;R14
為單鍵、或直鏈狀或分支狀之碳數1~6之伸烷基,且其碳原子之一部分也可取代為醚基或酯基;q為1或2;r為0~4之整數。 5. 如4之光阻材料,更含有溶解抑制劑。 6. 如4或5之光阻材料,其係化學增幅正型光阻材料。 7. 如1~3中任一項之光阻材料,其中,前述基礎聚合物不含酸不穩定基。 8. 如7之光阻材料,更含有交聯劑。 9. 如7或8之光阻材料,其係化學增幅負型光阻材料。 10. 如1~9中任一項之光阻材料,更含有界面活性劑。 11. 如1~10中任一項之光阻材料,其中,前述基礎聚合物更包含選自於下式(f1)~(f3)表示之重複單元中之至少1種。 [化3]式中,RA
各自獨立地為氫原子或甲基;Z1
為單鍵、伸苯基、-O-Z12
-、或-C(=O)-Z11
-Z12
-,Z11
為-O-或-NH-,Z12
為直鏈狀或分支狀或環狀之碳數1~6之伸烷基或碳數2~6之伸烯基、或伸苯基,且也可含有羰基、酯基、醚基或羥基;R31
~R38
各自獨立地為也可含有羰基、酯基或醚基之直鏈狀或分支狀或環狀之碳數1~12之烷基、或碳數6~12之芳基或碳數7~20之芳烷基,且它們的氫原子之一部分或全部也可取代為直鏈狀或分支狀或環狀之碳數1~10之烷基、鹵素原子、三氟甲基、氰基、硝基、羥基、巰基、直鏈狀或分支狀或環狀之碳數1~10之烷氧基、直鏈狀或分支狀或環狀之碳數2~10之烷氧基羰基、或直鏈狀或分支狀或環狀之碳數2~10之醯氧基;又,也可R33
、R34
及R35
中之任2個或R36
、R37
及R38
中之任2個互相鍵結並和它們所鍵結的硫原子一起形成環;Z2
為單鍵、-Z21
-C(=O)-O-、-Z21
-O-或-Z21
-O-C(=O)-,Z21
為直鏈狀或分支狀或環狀之碳數1~12之伸烷基,且也可含有羰基、酯基或醚基;A為氫原子或三氟甲基;Z3
為單鍵、亞甲基、伸乙基、伸苯基、氟化伸苯基、-O-Z32
-或-C(=O)-Z31
-Z32
-,Z31
為-O-或-NH-,Z32
為直鏈狀或分支狀或環狀之碳數1~6之伸烷基、伸苯基、氟化伸苯基、經三氟甲基取代之伸苯基、或直鏈狀或分支狀或環狀之碳數2~6之伸烯基,且也可含有羰基、酯基、醚基或羥基;M-
為非親核性相對離子。 12. 一種圖案形成方法,包含:將如1~11中任一項之光阻材料塗佈於基板上並進行加熱處理而形成光阻膜之步驟、將前述光阻膜以高能射線進行曝光之步驟、及使用顯影液將已曝光之光阻膜進行顯影之步驟。 13. 如12之圖案形成方法,其中,前述高能射線為波長193nm之ArF準分子雷射或波長248nm之KrF準分子雷射。 14. 如12之圖案形成方法,其中,前述高能射線為電子束(EB)或波長3~15nm之EUV。 [發明之效果]
經和碘化苯甲酸鍵結的氟苯磺酸之鋶鹽或錪鹽,由於碘的分子量大,故具有酸擴散小的特徵。此外,碘對於波長13.5nm之EUV之吸收非常大,故在曝光中,從碘會產生2次電子並使其高感度化。憑藉上述而可建構出高感度、低LWR且低CDU之光阻。
[光阻材料] 本發明之光阻材料包含:基礎聚合物,及含有經和碘化苯甲酸鍵結的氟苯磺酸之鋶鹽或錪鹽之酸產生劑。前述鋶鹽及錪鹽係因照光而產生經和碘化苯甲酸鍵結的氟苯磺酸之酸產生劑。本發明之光阻材料中亦可添加與上述酸產生劑不同的會產生磺酸、醯亞胺酸或甲基化酸(methide acid)之酸產生劑,也可和鍵結於基礎聚合物之結合型(bound-type)酸產生劑組合。
將前述經和碘化苯甲酸鍵結的氟苯磺酸之鋶鹽,及比起前述為弱酸之磺酸或羧酸的鋶鹽,以混合的狀態實施照光的話,會產生經和碘化苯甲酸鍵結的氟苯磺酸、及比起前述為弱酸之磺酸或羧酸。酸產生劑並非全部都會分解,故於周遭會存在有未分解之酸產生劑。在此,經和碘化苯甲酸鍵結的氟苯磺酸若與比起前述為弱酸之磺酸及羧酸的鋶鹽共存的話,經和碘化苯甲酸鍵結的氟苯磺酸會和弱酸之磺酸及羧酸的鋶鹽發生離子交換,並生成經和碘化苯甲酸鍵結的氟苯磺酸之鋶鹽,並釋放出弱酸之磺酸、羧酸。原因是就酸而言強度高的經和碘化苯甲酸鍵結的氟苯磺酸鹽較安定。另一方面,經和碘化苯甲酸鍵結的氟苯磺酸之鋶鹽即使和弱酸之磺酸、羧酸共存也不會發生離子交換。此根據酸強度排列所發生的離子交換不僅在鋶鹽,在錪鹽的情況也同樣會發生。作為氟磺酸之酸產生劑而予以組合時,弱酸之鋶鹽、錪鹽會作為淬滅劑而發揮功能。又,碘對於波長13.5nm之EUV的吸收極高,故在曝光中會產生2次電子,因2次電子之能量轉移會促進酸產生劑分解,並藉此達到高感度化。尤其碘的取代數為3以上時,此效果較高。
為了改善LWR,抑制聚合物、酸產生劑的凝聚係為有效。為了抑制聚合物的凝聚,減少疏水性與親水性的差、降低玻璃轉移點(Tg)、及降低聚合物的分子量中之任一者係為有效。具體而言,減少疏水性之酸不穩定基與親水性之黏合性基的極性差、使用如單環之內酯般緻密的黏合性基來降低Tg等係為有效。就抑制酸產生劑的凝聚而言,在三苯基鋶之陽離子部分導入取代基等係為有效。尤其,對於以脂環族保護基與內酯之黏合性基形成的ArF用之甲基丙烯酸酯聚合物而言,僅以芳香族基形成的三苯基鋶係異質結構,相容性低。就導入到三苯基鋶之取代基而言,可考慮與基礎聚合物所使用者相同之脂環族基或內酯。鋶鹽係親水性,故導入了內酯時,親水性會變得過高,而與聚合物之相容性會降低,造成鋶鹽的凝聚。若導入疏水性之烷基,較能將鋶鹽均勻分散於光阻膜內。國際公開第2011/048919號有人提出:將烷基導入到會產生α位經氟化之磺醯亞胺酸之鋶鹽以使LWR改善之方法。
前述經和碘化苯甲酸鍵結的氟苯磺酸之鋶鹽、錪鹽在陰離子部分導入有原子量大的碘,故擴散小且和聚合物之相容性高,因此分散性優良,藉此而改善LWR、CDU。
由於前述經和碘化苯甲酸鍵結的氟苯磺酸之鋶鹽、錪鹽所獲致之LWR、CDU之改善效果,無論在利用鹼水溶液顯影所為之正圖案形成、負圖案形成、或有機溶劑顯影時的負圖案形成中任一者均為有效。
[酸產生劑] 本發明之光阻材料所含的酸產生劑含有下式(A-1)表示之鋶鹽或下式(A-2)表示之錪鹽。 [化4]
式中,R1
為羥基、羧基、氟原子、氯原子、溴原子或胺基、或也可含有氟原子、氯原子、溴原子、羥基、胺基或烷氧基之直鏈狀或分支狀或環狀之碳數1~20之烷基、碳數1~20之烷氧基、碳數2~20之烷氧基羰基或碳數2~20之醯氧基、或-NR9
-C(=O)-R10
或-NR9
-C(=O)-O-R10
,R9
為氫原子,或直鏈狀或分支狀或環狀之碳數1~6之烷基,R10
為直鏈狀或分支狀或環狀之碳數1~16之烷基、直鏈狀或分支狀或環狀之碳數2~16之烯基、或碳數6~12之芳基,且也可含有鹵素原子、羥基、烷氧基、醯基或醯氧基;R2
為單鍵、或也可含有氧原子、硫原子或氮原子之碳數1~20之2價連結基;Rf
為氟原子或三氟甲基;R3
、R4
及R5
各自獨立地為氟原子、氯原子、溴原子、碘原子、直鏈狀或分支狀或環狀之碳數1~12之烷基、直鏈狀或分支狀或環狀之碳數2~12之烯基、碳數6~20之芳基、或碳數7~12之芳烷基或芳氧基烷基,且這些基的氫原子之一部分或全部也可取代為羥基、羧基、鹵素原子、側氧基、氰基、醯胺基、硝基、磺內酯基、碸基或含有鋶鹽之基,這些基的碳原子之一部分也可取代為醚基、酯基、羰基、碳酸酯基或磺酸酯基;又,也可R3
與R4
鍵結並和它們所鍵結的硫原子一起形成環;R6
及R7
為碳數6~10之芳基、碳數2~6之烯基、碳數2~6之炔基或三氟甲基,且這些基的氫原子之一部分或全部也可取代為鹵素原子、三氟甲基、直鏈狀或分支狀或環狀之碳數1~10之烷基或烷氧基、羥基、羧基、烷氧基羰基、硝基或氰基;m為1~5之整數;n為0~3之整數;p為1~4之整數。
作為式(A-1)表示之鋶鹽之陽離子部分可列舉如下所示,但不限於它們。 [化5]
[化6]
[化7]
[化8]
[化9]
[化10]
[化11]
[化12]
[化13]
[化14]
作為式(A-2)表示之錪鹽之陽離子部分可列舉如下所示,但不限於它們。 [化15]
作為式(A-1)表示之鋶鹽及式(A-2)表示之錪鹽之陰離子部分可列舉如下所示,但不限於它們。 [化16]
[化17]
[化18]
[化19]
[化20]
[化21]
作為式(A-1)表示之鋶鹽及式(A-2)表示之錪鹽之合成方法可例舉:和比起經鍵結於碘化苯甲酸的氟苯磺酸為弱酸之鋶鹽或錪鹽進行離子交換的方法。作為比起經鍵結於碘化苯甲酸的氟苯磺酸為弱酸之酸可列舉:碳酸、鹽酸、羧酸等。又,也可將經鍵結於碘化苯甲酸的氟苯磺酸之鈉鹽、銨鹽,和氯化鋶鹽或氯化錪鹽進行離子交換來合成。
在本發明之光阻材料中,考慮感度與酸擴散抑制效果的觀點,式(A-1)表示之鋶鹽或式(A-2)表示之錪鹽之含量相對於後述之基礎聚合物100質量份,宜為0.01~1,000質量份,為0.05~500質量份更佳。
[基礎聚合物] 本發明之光阻材料所含之基礎聚合物,在正型光阻材料的情況,包含含有酸不穩定基之重複單元。就含有酸不穩定基之重複單元而言,宜為下式(a1)表示之重複單元(以下稱重複單元a1)、或下式(a2)表示之重複單元(以下稱重複單元a2)。 [化22]
式中,RA
各自獨立地為氫原子或甲基;X1
為單鍵、伸苯基或伸萘基、或含有選自於酯基及內酯環中之至少1者之碳數1~12之連結基;X2
為單鍵或酯基;R11
及R12
為酸不穩定基;R13
為氟原子、三氟甲基、氰基、直鏈狀或分支狀或環狀之碳數1~6之烷基或烷氧基、或直鏈狀或分支狀或環狀之碳數2~7之醯基、醯氧基或烷氧基羰基;R14
為單鍵、或直鏈狀或分支狀之碳數1~6之伸烷基,且其碳原子之一部分也可取代為醚基或酯基;q為1或2;r為0~4之整數。
作為重複單元a1可列舉如下所示,但不限於它們。另外,下式中,RA
及R11
係如前所述。 [化23]
作為重複單元a2可列舉如下所示,但不限於它們。另外,下式中,RA
及R12
係如前所述。 [化24]
式(a1)及(a2)中,作為R11
及R12
表示之酸不穩定基可列舉例如:日本特開2013-80033號公報、日本特開2013-83821號公報所記載者。
就代表性而言,作為前述酸不穩定基可列舉下式(AL-1)~(AL-3)表示者。 [化25]
式(AL-1)及(AL-2)中,R15
及R18
為直鏈狀或分支狀或環狀之烷基等之碳數1~40,宜為1~20之1價烴基,且也可含有氧原子、硫原子、氮原子、氟原子等雜原子。R16
及R17
各自獨立地為氫原子、或直鏈狀或分支狀或環狀之烷基等之碳數1~20之1價烴基,且也可含有氧原子、硫原子、氮原子、氟原子等雜原子。又,也可R16
、R17
及R18
中之任2個互相鍵結並和它們所鍵結的碳原子或碳原子及氧原子一起形成碳數3~20,宜為4~16的環,形成脂環特佳。A1為0~10,宜為1~5之整數。
式(AL-3)中,R19
、R20
及R21
各自獨立地為直鏈狀或分支狀或環狀之烷基等之碳數1~20之1價烴基,且也可含有氧原子、硫原子、氮原子、氟原子等雜原子。又,也可R19
、R20
及R21
中之任2個互相鍵結並和它們所鍵結的碳原子一起形成碳數3~20,宜為4~16的環,形成脂環特佳。
前述基礎聚合物也可更包含含有苯酚性羥基作為黏合性基之重複單元b。作為提供重複單元b之單體可列舉如下所示,但不限於它們。另外,下式中,RA
係如前所述。
[化26]
前述基礎聚合物也可更包含含有苯酚性羥基以外之羥基、羧基、內酯環、醚基、酯基、羰基或氰基作為其他黏合性基之重複單元c。作為提供重複單元c之單體可列舉如下所示,但不限於它們。另外,下式中,RA
係如前所述。
[化27]
[化28]
[化29]
[化30]
[化31]
[化32]
[化33]
[化34]
含有羥基之單體的情況,聚合時可事先將羥基以乙氧基乙氧基(ethoxyethoxy)等容易因酸而脫保護之縮醛基取代,並於聚合後利用弱酸與水來實施脫保護;亦可事先以乙醯基、甲醯基、三甲基乙醯基等予以取代,並於聚合後實施鹼水解。
前述基礎聚合物也可更包含源自茚、苯并呋喃、苯并噻吩、苊、色酮、香豆素、降莰二烯或它們的衍生物之重複單元d。作為提供重複單元d之單體可列舉如下所示,但不限於它們。
[化35]
前述基礎聚合物也可更包含源自苯乙烯、乙烯基萘、乙烯基蒽、乙烯基芘、亞甲基二氫茚、乙烯基吡啶或乙烯基咔唑之重複單元e。
前述基礎聚合物也可更包含源自含有聚合性不飽和鍵之鎓鹽之重複單元f。作為理想的重複單元f可列舉:下式(f1)表示之重複單元(以下稱重複單元f1)、下式(f2)表示之重複單元(以下稱重複單元f2)、及下式(f3)表示之重複單元(以下稱重複單元f3)。另外,重複單元f1~f3可單獨使用1種,也可將2種以上組合使用。
[化36]
式中,RA
各自獨立地為氫原子或甲基;Z1
為單鍵、伸苯基、-O-Z12
-、或-C(=O)-Z11
-Z12
-,Z11
為-O-或-NH-,Z12
為直鏈狀或分支狀或環狀之碳數1~6之伸烷基或碳數2~6之伸烯基、或伸苯基,且也可含有羰基、酯基、醚基或羥基;R31
~R38
各自獨立地為也可含有羰基、酯基或醚基之直鏈狀或分支狀或環狀之碳數1~12之烷基、或碳數6~12之芳基或碳數7~20之芳烷基,且它們的氫原子之一部分或全部也可取代為直鏈狀或分支狀或環狀之碳數1~10之烷基、鹵素原子、三氟甲基、氰基、硝基、羥基、巰基、直鏈狀或分支狀或環狀之碳數1~10之烷氧基、直鏈狀或分支狀或環狀之碳數2~10之烷氧基羰基、或直鏈狀或分支狀或環狀之碳數2~10之醯氧基;又,也可R33
、R34
及R35
中之任2個或R36
、R37
及R38
中之任2個互相鍵結並和它們所鍵結的硫原子一起形成環;Z2
為單鍵、-Z21
-C(=O)-O-、-Z21
-O-或-Z21
-O-C(=O)-,Z21
為直鏈狀或分支狀或環狀之碳數1~12之伸烷基,且也可含有羰基、酯基或醚基;A為氫原子或三氟甲基;Z3
為單鍵、亞甲基、伸乙基、伸苯基、氟化伸苯基、-O-Z32
-或-C(=O)-Z31
-Z32
-,Z31
為-O-或-NH-,Z32
為直鏈狀或分支狀或環狀之碳數1~6之伸烷基、伸苯基、氟化伸苯基、經三氟甲基取代之伸苯基、或直鏈狀或分支狀或環狀之碳數2~6之伸烯基,且也可含有羰基、酯基、醚基或羥基;M-
為非親核性相對離子。
作為提供重複單元f1之單體可列舉如下所示,但不限於它們。另外,下式中,RA
及M-
係如前所述。 [化37]
作為M-
表示之非親核性相對離子可列舉:氯化物離子、溴化物離子等之鹵化物離子;三氟甲磺酸鹽離子、1,1,1-三氟乙磺酸鹽離子、九氟丁磺酸鹽離子等之氟烷基磺酸鹽離子;甲苯磺酸鹽離子、苯磺酸鹽離子、4-氟苯磺酸鹽離子、1,2,3,4,5-五氟苯磺酸鹽離子等之芳基磺酸鹽離子;甲磺酸鹽離子、丁磺酸鹽離子等之烷基磺酸鹽離子;雙(三氟甲基磺醯基)醯亞胺離子、雙(全氟乙基磺醯基)醯亞胺離子、雙(全氟丁基磺醯基)醯亞胺離子等之醯亞胺酸離子;參(三氟甲基磺醯基)甲基化物離子、參(全氟乙基磺醯基)甲基化物離子等之甲基化酸離子。
作為前述非親核性相對離子更可列舉:下式(K-1)表示之α位經氟取代之磺酸離子、下式(K-2)表示之α及β位經氟取代之磺酸離子等。 [化38]
式(K-1)中,R51
係氫原子、直鏈狀或分支狀或環狀之碳數1~20之烷基、直鏈狀或分支狀或環狀之碳數2~20之烯基、或碳數6~20之芳基,且也可含有醚基、酯基、羰基、內酯環或氟原子。
式(K-2)中,R52
係氫原子、直鏈狀或分支狀或環狀之碳數1~30之烷基、直鏈狀或分支狀或環狀之碳數2~20之醯基、直鏈狀或分支狀或環狀之碳數2~20之烯基、碳數6~20之芳基、或碳數6~20之芳氧基,且也可含有醚基、酯基、羰基或內酯環。
作為提供重複單元f2之單體可列舉如下所示,但不限於它們。另外,下式中,RA
係如前所述。 [化39]
[化40]
[化41]
[化42]
作為提供重複單元f3之單體可列舉如下所示,但不限於它們。另外,下式中,RA
係如前所述。 [化43]
[化44]
[化45]
藉由使酸產生劑鍵結於聚合物主鏈可減少酸擴散,並防止因酸擴散的模糊導致之解析度的降低。又,藉由酸產生劑均勻地分散,會改善邊緣粗糙度。
正型光阻材料用之基礎聚合物係以含有酸不穩定基之重複單元a1或a2為必須。此時,重複單元a1、a2、b、c、d、e及f之含有比率宜為0≦a1<1.0,0≦a2<1.0,0<a1+a2<1.0,0≦b≦0.9,0≦c≦0.9,0≦d≦0.8,0≦e≦0.8,及0≦f≦0.5,為0≦a1≦0.9,0≦a2≦0.9,0.1≦a1+a2≦0.9,0≦b≦0.8,0≦c≦0.8,0≦d≦0.7,0≦e≦0.7,及0≦f≦0.4更佳,為0≦a1≦0.8,0≦a2≦0.8,0.1≦a1+a2≦0.8,0≦b≦0.75,0≦c≦0.75,0≦d≦0.6,0≦e≦0.6,及0≦f≦0.3再更佳。另外,重複單元f係選自於重複單元f1~f3中之至少1種時,f=f1+f2+f3。又,a1+a2+b+c+d+e+f=1.0。
另一方面,負型光阻材料用之基礎聚合物則不必一定要有酸不穩定基。作為如此的基礎聚合物可列舉含有重複單元b,因應需要更含有重複單元c、d、e及/或f者。該等重複單元之含有比率宜為0<b≦1.0,0≦c≦0.9,0≦d≦0.8,0≦e≦0.8,及0≦f≦0.5,為0.2≦b≦1.0,0≦c≦0.8,0≦d≦0.7,0≦e≦0.7,及0≦f≦0.4更佳,為0.3≦b≦1.0,0≦c≦0.75,0≦d≦0.6,0≦e≦0.6,及0≦f≦0.3再更佳。另外,重複單元f係選自於重複單元f1~f3中之至少1種時,f=f1+f2+f3。又,b+c+d+e+f=1.0。
就合成前述基礎聚合物而言,例如將提供前述重複單元之單體在有機溶劑中添加自由基聚合起始劑後加熱並實施聚合即可。
作為聚合時所使用的有機溶劑可列舉:甲苯、苯、四氫呋喃、二***、二烷等。作為聚合起始劑可列舉:2,2'-偶氮雙異丁腈(AIBN)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2-偶氮雙(2-甲基丙酸)二甲酯、過氧化苯甲醯、過氧化月桂醯等。聚合時的溫度宜為50~80℃。反應時間宜為2~100小時,為5~20小時更佳。
將羥苯乙烯、羥乙烯基萘予以共聚合時,也可使用乙醯氧基苯乙烯、乙醯氧基乙烯基萘替代羥苯乙烯、羥乙烯基萘,並於聚合後利用前述鹼水解來將乙醯氧基脫保護而製成羥苯乙烯、羥乙烯基萘。
作為鹼水解時的鹼可使用:氨水、三乙胺等。又,反應溫度宜為-20~100℃,為0~60℃更佳。反應時間宜為0.2~100小時,為0.5~20小時更佳。
就前述基礎聚合物而言,以使用四氫呋喃(THF)作為溶劑之凝膠滲透層析法(GPC)獲得之聚苯乙烯換算重量平均分子量(Mw)宜為1,000~500,000,為2,000~30,000更佳。Mw過小的話,光阻材料之耐熱性不良,過大的話,鹼溶解性會降低,且圖案形成後容易發生拖尾現象。
此外,前述基礎聚合物中分子量分佈(Mw/Mn)較廣時,會存在低分子量、高分子量之聚合物,故於曝光後會存有在圖案上看見異物、或圖案的形狀惡化之顧慮。Mw、分子量分佈的影響容易隨圖案規則之微細化而變大,故為了獲得適用於微細的圖案尺寸之光阻材料,前述基礎聚合物之分子量分佈宜為1.0~2.0,尤其宜為1.0~1.5之狹窄分散。
前述基礎聚合物也可含有組成比率、Mw、分子量分佈不同的2種以上之聚合物。
[淬滅劑] 本發明之光阻材料中也可摻合淬滅劑。作為前述淬滅劑可列舉習知類型的鹼性化合物。作為習知類型的鹼性化合物可列舉:一級、二級、三級脂肪族胺類、混成胺類、芳香族胺類、雜環胺類、含有羧基之含氮化合物、具有磺醯基之含氮化合物、具有羥基之含氮化合物、具有羥苯基之含氮化合物、醇性含氮化合物、醯胺類、醯亞胺類、胺基甲酸酯類等。尤其宜為日本特開2008-111103號公報之段落[0146]~[0164]所記載之一級、二級、三級胺化合物,為具有羥基、醚基、酯基、內酯環、氰基、磺酸酯基之胺化合物或日本專利第3790649號公報所記載之具有胺基甲酸酯基之化合物等特佳。藉由添加如此的鹼性化合物,例如可更抑制光阻膜中之酸的擴散速度、或可修正形狀。
又,作為前述淬滅劑可列舉日本特開2008-158339號公報所記載之α位未氟化之磺酸的鋶鹽、錪鹽、銨鹽等之鎓鹽。α位經氟化之磺酸、醯亞胺酸或甲基化酸在使羧酸酯之酸不穩定基脫保護時係為必要,而利用和α位未氟化之鎓鹽的鹽交換會放出α位未氟化之磺酸。α位未氟化之磺酸不會引起脫保護反應,故作為淬滅劑而發揮功能。
作為前述淬滅劑更可列舉日本特開2008-239918號公報所記載之聚合物型淬滅劑。該聚合物型淬滅劑係藉由配向於塗佈後之光阻表面來提高圖案化後之光阻的矩形性。聚合物型淬滅劑也有防止使用浸潤式曝光用之保護膜時之圖案之膜損失、圖案之圓頂化的效果。
此外,下式(1)表示之羧酸鎓鹽也適合使用作為淬滅劑。 [化46]
式中,R101
表示也可含有雜原子之直鏈狀或分支狀或環狀之碳數1~40之1價烴基。MA +
表示鎓離子。作為前述鎓離子可列舉:鋶離子、錪離子、銨離子等。
作為前述羧酸鎓鹽之陰離子部分宜為下式(2)表示者。 [化47]
R102
及R103
各自獨立地表示氫原子、氟原子或三氟甲基。R104
表示氫原子、羥基、也可含有雜原子之直鏈狀或分支狀或環狀之碳數1~35之1價烴基、或有取代或無取代之碳數6~30之芳基。
作為前述羧酸鎓鹽可列舉如下所示,但不限於它們。 [化48]
[化49]
[化50]
[化51]
[化52]
本發明之光阻材料含有淬滅劑時,其含量相對於基礎聚合物100質量份,宜為0.1~20質量份,為0.2~10質量份更佳。
[其他成分] 除了摻合前述成分之外,更可因應目的適當組合並摻合有機溶劑、界面活性劑、溶解抑制劑、交聯劑等來構成正型光阻材料及負型光阻材料,藉此在曝光部,前述基礎聚合物由於觸媒反應而對顯影液之溶解速度會加速,故可製成極高感度之正型光阻材料及負型光阻材料。此時,光阻膜之溶解對比度及解析度高,具有曝光允差,製程適應性優良,曝光後之圖案形狀良好,而且尤其因為可抑制酸擴散,故疏密尺寸差小,基於這些優點,可製成實用性高,就超大型積體電路用光阻材料而言非常有效者。尤其,製成利用了酸觸媒反應之化學增幅正型光阻材料的話,可製成更高感度者,同時成為諸特性更為優良者,而極為有效。
本發明之光阻材料在不損及本發明之效果之範圍內,也可包含式(A-1)表示之鋶鹽或式(A-2)表示之錪鹽以外的酸產生劑(以下稱其他酸產生劑)。作為其他酸產生劑可列舉:感應活性光線或放射線而產生酸的化合物(光酸產生劑)。就光酸產生劑的成分而言,若為利用高能射線照射而產生酸的化合物,則為任意均無妨,但宜為產生磺酸、醯亞胺酸或甲基化酸之酸產生劑。就理想的光酸產生劑而言,有鋶鹽、錪鹽、磺醯基重氮甲烷、N-磺醯氧基醯亞胺、肟-O-磺酸酯型酸產生劑等。就酸產生劑之具體例而言,係如日本特開2008-111103號公報之段落[0122]~[0142]所記載。其他酸產生劑之含量相對於基礎聚合物100質量份,宜為0~200質量份,為0.1~100質量份更佳。
正型光阻材料的情況,藉由摻合溶解抑制劑,可進一步加大曝光部與未曝光部之溶解速度差,可使解析度更改善。負型光阻材料的情況,藉由添加交聯劑,可使曝光部之溶解速度降低並藉此獲得負圖案。
作為前述有機溶劑可列舉日本特開2008-111103號公報之段落[0144]~[0145]所記載之環己酮、環戊酮、甲基-2-正戊酮等之酮類;3-甲氧基丁醇、3-甲基-3-甲氧基丁醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇等之醇類;丙二醇單甲醚、乙二醇單甲醚、丙二醇單***、乙二醇單***、丙二醇二甲醚、二乙二醇二甲醚等之醚類;丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、乳酸乙酯、丙酮酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸三級丁酯、丙酸三級丁酯、丙二醇單三級丁醚乙酸酯等之酯類;γ-丁內酯等之內酯類;以及它們的混合溶劑。
本發明之光阻材料中,前述有機溶劑之含量相對於基礎聚合物100質量份,宜為100~10,000質量份,為200~8,000質量份更佳。
作為前述界面活性劑可列舉日本特開2008-111103號公報之段落[0165]~[0166]所記載者。藉由添加界面活性劑,可進一步改善或控制光阻材料之塗佈性。本發明之光阻材料中,界面活性劑之含量相對於基礎聚合物100質量份,宜為0.0001~10質量份。
作為前述溶解抑制劑可列舉:分子量宜為100~1,000,更佳為150~800且分子內含有2個以上之苯酚性羥基之化合物之該苯酚性羥基之氫原子經以就整體而言為0~100莫耳%之比例取代為酸不穩定基而成之化合物、或分子內含有羧基之化合物之該羧基之氫原子經以就整體而言為平均50~100莫耳%之比例取代為酸不穩定基而成之化合物。具體而言可列舉雙酚A、參酚、酚酞、甲酚酚醛清漆樹脂、萘羧酸、金剛烷羧酸、膽酸(cholic acid)中之羥基、羧基之氫原子經取代為酸不穩定基而成之化合物等,例如日本特開2008-122932號公報之段落[0155]~[0178]所記載。
本發明之光阻材料為正型光阻材料時,溶解抑制劑之含量相對於基礎聚合物100質量份,宜為0~50質量份,為5~40質量份更佳。
作為交聯劑可列舉經選自於羥甲基、烷氧基甲基及醯氧基甲基中之至少1個基取代之環氧化合物、三聚氰胺化合物、胍胺化合物、甘脲(glycoluril)化合物或脲化合物、異氰酸酯化合物、疊氮化合物、含有烯基醚基等之雙鍵之化合物等。它們可作為添加劑使用,也可作為懸垂基(pendant group)而導入到聚合物側鏈中。又,含有羥基之化合物也可作為交聯劑使用。
作為前述環氧化合物可列舉:異氰尿酸參(2,3-環氧丙酯)、三羥甲基甲烷三環氧丙醚、三羥甲基丙烷三環氧丙醚、三羥乙基乙烷三環氧丙醚等。
作為前述三聚氰胺化合物可列舉:六羥甲基三聚氰胺、六甲氧基甲基三聚氰胺、六羥甲基三聚氰胺中之1~6個羥甲基經甲氧基甲基化而成的化合物或其混合物、六甲氧基乙基三聚氰胺、六醯氧基甲基三聚氰胺、六羥甲基三聚氰胺中之1~6個羥甲基經醯氧基甲基化而成的化合物或其混合物等。
作為胍胺化合物可列舉:四羥甲基胍胺、四甲氧基甲基胍胺、四羥甲基胍胺中之1~4個羥甲基經甲氧基甲基化而成的化合物或其混合物、四甲氧基乙基胍胺、四醯氧基胍胺、四羥甲基胍胺中之1~4個羥甲基經醯氧基甲基化而成的化合物或其混合物等。
作為甘脲化合物可列舉:四羥甲基甘脲、四甲氧基甘脲、四甲氧基甲基甘脲、四羥甲基甘脲中之1~4個羥甲基經甲氧基甲基化而成的化合物或其混合物、四羥甲基甘脲中之1~4個羥甲基經醯氧基甲基化而成的化合物或其混合物等。作為脲化合物可列舉:四羥甲基脲、四甲氧基甲基脲、四羥甲基脲中之1~4個羥甲基經甲氧基甲基化而成的化合物或其混合物、四甲氧基乙基脲等。
作為異氰酸酯化合物可列舉:二異氰酸甲苯酯、二苯基甲烷二異氰酸酯、二異氰酸六亞甲酯、環己烷二異氰酸酯等。
作為疊氮化合物可列舉:1,1'-聯苯-4,4'-雙疊氮化物、4,4'-亞甲基雙疊氮化物、4,4'-氧基雙疊氮化物等。
作為含有烯基醚基之化合物可列舉:乙二醇二乙烯基醚、三乙二醇二乙烯基醚、1,2-丙二醇二乙烯基醚、1,4-丁二醇二乙烯基醚、四亞甲基二醇二乙烯基醚、新戊二醇二乙烯基醚、三羥甲基丙烷三乙烯基醚、己二醇二乙烯基醚、1,4-環己二醇二乙烯基醚、新戊四醇三乙烯基醚、新戊四醇四乙烯基醚、山梨糖醇四乙烯基醚、山梨糖醇五乙烯基醚、三羥甲基丙烷三乙烯基醚等。
本發明之光阻材料為負型光阻材料的情況,交聯劑之含量相對於基礎聚合物100質量份,宜為0.1~50質量份,為1~40質量份更佳。
本發明之光阻材料中也可摻合用來改善旋塗後之光阻表面的撥水性之高分子化合物(撥水性改善劑)。前述撥水性改善劑可使用在未利用表面塗層(top coat)之浸潤式微影。就前述撥水性改善劑而言,宜為含有氟化烷基之高分子化合物、具有特定結構之含有1,1,1,3,3,3-六氟-2-丙醇殘基之高分子化合物等,為日本特開2007-297590號公報、日本特開2008-111103號公報等所例示者更佳。前述撥水性改善劑必須溶解於有機溶劑顯影液中。前述特定之具有1,1,1,3,3,3-六氟-2-丙醇殘基之撥水性改善劑溶解到顯影液中之溶解性良好。就撥水性改善劑而言,包括含有胺基、胺鹽之重複單元之高分子化合物,其防止PEB中之酸的蒸發進而防止顯影後之孔洞圖案的開口不良之效果高。本發明之光阻材料中,撥水性改善劑之含量相對於基礎聚合物100質量份,宜為0~20質量份,為0.5~10質量份更佳。
本發明之光阻材料中,也可摻合乙炔醇類。作為前述乙炔醇類可列舉日本特開2008-122932號公報之段落[0179]~[0182]所記載者。本發明之光阻材料中,乙炔醇類之含量相對於基礎聚合物100質量份,宜為0~5質量份。
[圖案形成方法] 將本發明之光阻材料使用於各種積體電路製造時,可使用公知的微影技術。
例如,將本發明之正型光阻材料利用旋塗、輥塗、流塗、浸塗、噴塗、刮塗等適當的塗佈方法塗佈於積體電路製造用之基板(Si、SiO2
、SiN、SiON、TiN、WSi、BPSG、SOG、有機抗反射膜等)或遮罩電路製造用之基板(Cr、CrO、CrON、MoSi2
、SiO2
等)上,並使其塗佈膜厚成為0.01~2.0μm。將其於加熱板上宜以60~150℃、10秒~30分鐘條件預烘,以80~120℃、30秒~20分鐘條件預烘更佳。然後,利用紫外線、遠紫外線、EB、EUV、X射線、軟X射線、準分子雷射、γ射線、同步輻射等高能射線,將成為目的之圖案通過預定的遮罩或直接實施曝光。曝光量約為1~200mJ/cm2
,尤其宜以約10~100mJ/cm2
、或約0.1~100μC/cm2
進行曝光,以成為約0.5~50μC/cm2
的方式進行曝光特佳。然後,於加熱板上宜以60~150℃、10秒~30分鐘條件進行PEB,以80~120℃、30秒~20分鐘條件進行PEB更佳。
進一步使用0.1~10質量%,宜為2~5質量%之四甲基氫氧化銨(TMAH)、四乙基氫氧化銨(TEAH)、四丙基氫氧化銨(TPAH)、四丁基氫氧化銨(TBAH)等之鹼水溶液之顯影液,以3秒~3分鐘條件,宜以5秒~2分鐘條件,利用浸漬(dip)法、浸置(puddle)法、噴霧(spray)法等常用方法進行顯影,藉此已照光的部分會溶解於顯影液,未曝光部分則不溶解而於基板上形成為目的之正型圖案。負型光阻的情況則與正型光阻的情況相反,亦即已照光的部分不溶於顯影液,未曝光部分則會溶解。另外,本發明之光阻材料最適於尤其高能射線之中KrF準分子雷射、ArF準分子雷射、EB、EUV、X射線、軟X射線、γ射線、同步輻射所為之微細圖案化。
也可使用包括含有酸不穩定基之基礎聚合物之正型光阻材料並利用有機溶劑顯影來實施會獲得負圖案之負顯影。作為此時使用的顯影液可列舉:2-辛酮、2-壬酮、2-庚酮、3-庚酮、4-庚酮、2-己酮、3-己酮、二異丁酮、甲基環己酮、苯乙酮、甲基苯乙酮、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙酸戊酯、乙酸丁烯酯、乙酸異戊酯、甲酸丙酯、甲酸丁酯、甲酸異丁酯、甲酸戊酯、甲酸異戊酯、戊酸甲酯、戊烯酸甲酯、巴豆酸甲酯、巴豆酸乙酯、丙酸甲酯、丙酸乙酯、3-乙氧基丙酸乙酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、乳酸異丁酯、乳酸戊酯、乳酸異戊酯、2-羥異丁酸甲酯、2-羥異丁酸乙酯、苯甲酸甲酯、苯甲酸乙酯、乙酸苯酯、乙酸苄酯、苯乙酸甲酯、甲酸苄酯、甲酸苯乙酯、3-苯丙酸甲酯、丙酸苄酯、苯乙酸乙酯、乙酸-2-苯乙酯等。該等有機溶劑可單獨使用1種,也可將2種以上混合使用。
顯影結束時實施沖洗。就沖洗液而言,宜為與顯影液混溶且不溶解光阻膜之溶劑。宜使用碳數3~10之醇、碳數8~12之醚化合物、碳數6~12之烷、烯、炔、芳香族系之溶劑作為如此的溶劑。
具體而言,作為碳數3~10之醇可列舉:正丙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、三級丁醇、1-戊醇、2-戊醇、3-戊醇、三級戊醇、新戊醇、2-甲基-1-丁醇、3-甲基-1-丁醇、3-甲基-3-戊醇、環戊醇、1-己醇、2-己醇、3-己醇、2,3-二甲基-2-丁醇、3,3-二甲基-1-丁醇、3,3-二甲基-2-丁醇、2-乙基-1-丁醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-甲基-3-戊醇、3-甲基-1-戊醇、3-甲基-2-戊醇、3-甲基-3-戊醇、4-甲基-1-戊醇、4-甲基-2-戊醇、4-甲基-3-戊醇、環己醇、1-辛醇等。
作為碳數8~12之醚化合物可列舉選自於二正丁醚、二異丁醚、二(二級丁醚)、二正戊醚、二異戊醚、二(二級戊醚)、二(三級戊醚)、二正己醚中之1種以上之溶劑。
作為碳數6~12之烷可列舉:己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、甲基環戊烷、二甲基環戊烷、環己烷、甲基環己烷、二甲基環己烷、環庚烷、環辛烷、環壬烷等。作為碳數6~12之烯可列舉:己烯、庚烯、辛烯、環己烯、甲基環己烯、二甲基環己烯、環庚烯、環辛烯等。作為碳數6~12之炔可列舉:己炔、庚炔、辛炔等。
作為芳香族系之溶劑可列舉:甲苯、二甲苯、乙苯、異丙苯、三級丁苯、均三甲苯等。
藉由實施沖洗可使光阻圖案之崩塌、缺陷的發生減少。又,沖洗並非一定需要,藉由不實施沖洗可減少溶劑的使用量。
也可將顯影後之孔洞圖案、溝圖案以熱流(thermal flow)、RELACS技術或DSA技術進行收縮。將收縮劑塗佈於孔洞圖案上,由於烘烤中來自光阻層之酸觸媒的擴散,在光阻的表面引發收縮劑之交聯,收縮劑會附著於孔洞圖案之側壁。烘烤溫度宜為70~180℃,為80~170℃更佳,時間宜為10~300秒,將多餘的收縮劑去除並使孔洞圖案縮小。 [實施例]
以下,展示合成例、實施例及比較例來具體地說明本發明,但本發明不限於下述實施例。
本發明之光阻材料所使用的由鋶鹽或錪鹽構成的酸產生劑PAG1~12之結構如下所示。PAG1~12係各別利用賦予下述陰離子之經鍵結於碘化苯甲酸的氟苯磺酸之銨鹽,與賦予下述陽離子之氯化鋶或氯化錪的離子交換來合成。 [化53]
[化54]
[合成例]基礎聚合物(聚合物1~3)之合成 將各別的單體組合並於四氫呋喃(THF)溶劑下實施共聚合反應,於甲醇中析出結晶,再利用己烷重複清洗後,進行分離、乾燥,獲得如下所示之組成的基礎聚合物(聚合物1~3)。得到的基礎聚合物之組成係利用1
H-NMR進行確認,Mw及分散度(Mw/Mn)係利用GPC(溶劑:THF,標準品:聚苯乙烯)進行確認。
[化55]
[實施例、比較例] 將使各成分以表1及2所示之組成溶解於溶劑中而成的溶液,以0.2μm孔徑尺寸之過濾器進行過濾,製得光阻材料,該溶劑係已使作為界面活性劑之3M公司製FC-4430溶解100ppm而得。
表1及2中,各成分如下所示。 有機溶劑: PGMEA(丙二醇單甲醚乙酸酯) GBL(γ-丁內酯) CyH(環己酮) PGME(丙二醇單甲醚) DAA(二丙酮醇)
比較酸產生劑:比較PAG1~4(參照下述結構式) [化56]
淬滅劑1~3(參照下述結構式) [化57]
撥水劑聚合物1~2(參照下述結構式) [化58]
[ArF浸潤式曝光評價] [實施例1-1~1-10、比較例1-1~1-4] 將表1所示之各光阻材料旋轉塗佈於基板上,該基板係於矽晶圓上成膜有信越化學工業(股)製旋塗式碳膜ODL-102(碳含量為80質量%)200nm,並於其上以35nm之膜厚成膜有含矽之旋塗式硬遮罩SHB-A940(矽含量為43質量%)之三層處理用基板,再使用加熱板於100℃烘烤60秒,製得膜厚80nm之光阻膜。使用ArF準分子雷射掃描式曝光機(Nikon(股)製NSR-S610C,NA1.30,σ0.98/0.78,35度交叉極照明,Azimuthally偏光照明,6%半階調相位偏移遮罩),並使用晶圓上尺寸為50nm線(line)、100nm節距(pitch)之遮罩將上述光阻膜進行浸潤式曝光,並於表1所記載之溫度實施60秒PEB。另外,使用水作為浸潤液。實施例1-1~1-9及比較例1-1~1-3係以乙酸正丁酯實施30秒顯影,實施例1-10及比較例1-4係以2.38質量%TMAH水溶液進行顯影,形成尺寸為50nm間距(space)、100nm節距(pitch)之線與間距(line-and-space)之負型圖案。使用Hitachi High-Technologies Corporation(股)製測長SEM(CG4000),測定以1:1形成線與間距圖案時的曝光量,並令其為感度,又,測定此時的邊緣粗糙度(LWR)。結果如表1所示。
[表1]
[EUV曝光評價] [實施例2-1~2-6、比較例2-1] 將表2所示之各光阻材料旋塗於Si基板上,該Si基板係將信越化學工業(股)製含矽之旋塗式硬遮罩SHB-A940(矽含量為43質量%)以20nm膜厚形成而成,再使用加熱板於105℃預烘60秒,製得膜厚60nm之光阻膜。使用ASML公司製EUV掃描式曝光機NXE3300(NA0.33,σ0.9/0.6,四極照明,晶圓上尺寸為節距46nm,+20%偏差之孔洞圖案之遮罩)對上述光阻膜進行曝光,並使用加熱板以表2所記載之溫度實施60秒PEB,再於2.38質量%TMAH水溶液實施30秒顯影,形成尺寸23nm之孔洞圖案。使用Hitachi High-Technologies Corporation(股)製測長SEM(CG5000),測定以23nm形成孔洞尺寸時的曝光量,並令其為感度,又,求得此時之50個孔洞的尺寸變異(CDU,3σ)。結果如表2所示。
[表2]
由表1及2所示之結果可知:含有經鍵結於碘化苯甲酸的氟苯磺酸之鋶鹽或錪鹽作為酸產生劑之本發明之光阻材料,係高感度且LWR與CDU良好。
Claims (14)
- 一種光阻材料,包含:基礎聚合物,及含有下式(A-1)表示之鋶鹽或下式(A-2)表示之錪鹽之酸產生劑; [化1]
- 如申請專利範圍第1項之光阻材料,更含有淬滅劑。
- 如申請專利範圍第1或2項之光阻材料,更含有有機溶劑。
- 如申請專利範圍第1或2項之光阻材料,其中,該基礎聚合物包含下式(a1)表示之重複單元或下式(a2)表示之重複單元; [化2]
- 如申請專利範圍第4項之光阻材料,更含有溶解抑制劑。
- 如申請專利範圍第4項之光阻材料,其係化學增幅正型光阻材料。
- 如申請專利範圍第1或2項之光阻材料,其中,該基礎聚合物不含酸不穩定基。
- 如申請專利範圍第7項之光阻材料,更含有交聯劑。
- 如申請專利範圍第7項之光阻材料,其係化學增幅負型光阻材料。
- 如申請專利範圍第1或2項之光阻材料,更含有界面活性劑。
- 如申請專利範圍第1或2項之光阻材料,其中,該基礎聚合物更包含選自於下式(f1)~(f3)表示之重複單元中之至少1種; [化3]
- 一種圖案形成方法,包含下列步驟: 將如申請專利範圍第1至11項中任一項之光阻材料塗佈於基板上並進行加熱處理而形成光阻膜; 將該光阻膜以高能射線進行曝光;及 使用顯影液將已曝光之光阻膜進行顯影。
- 如申請專利範圍第12項之圖案形成方法,其中,該高能射線為波長193nm之ArF準分子雷射或波長248nm之KrF準分子雷射。
- 如申請專利範圍第12項之圖案形成方法,其中,該高能射線為電子束或波長3~15nm之極紫外線。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017-055799 | 2017-03-22 | ||
JP2017055799A JP6648726B2 (ja) | 2017-03-22 | 2017-03-22 | レジスト材料及びパターン形成方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201838972A true TW201838972A (zh) | 2018-11-01 |
TWI664162B TWI664162B (zh) | 2019-07-01 |
Family
ID=63581708
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW107109207A TWI664162B (zh) | 2017-03-22 | 2018-03-19 | 光阻材料及圖案形成方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US10613436B2 (zh) |
JP (1) | JP6648726B2 (zh) |
KR (1) | KR102078914B1 (zh) |
TW (1) | TWI664162B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI720792B (zh) * | 2019-01-25 | 2021-03-01 | 日商信越化學工業股份有限公司 | 光阻材料及圖案形成方法 |
TWI747201B (zh) * | 2019-03-22 | 2021-11-21 | 日商信越化學工業股份有限公司 | 光阻組成物及圖案形成方法 |
TWI781661B (zh) * | 2020-06-25 | 2022-10-21 | 日商信越化學工業股份有限公司 | 阻劑材料及圖案形成方法 |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6848767B2 (ja) * | 2016-09-27 | 2021-03-24 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
US10831100B2 (en) * | 2017-11-20 | 2020-11-10 | Rohm And Haas Electronic Materials, Llc | Iodine-containing photoacid generators and compositions comprising the same |
JP7010195B2 (ja) * | 2017-11-29 | 2022-01-26 | 信越化学工業株式会社 | パターン形成方法 |
JP7283955B2 (ja) * | 2018-04-12 | 2023-05-30 | 住友化学株式会社 | レジスト組成物及びレジストパターンの製造方法 |
KR20190135415A (ko) * | 2018-05-28 | 2019-12-06 | 도오꾜오까고오교 가부시끼가이샤 | 레지스트 조성물, 레지스트 패턴 형성 방법, 화합물, 산 발생제 및 화합물의 제조 방법 |
JP7247732B2 (ja) * | 2019-04-24 | 2023-03-29 | Jsr株式会社 | 感放射線性樹脂組成物、レジストパターン形成方法、感放射線性酸発生剤及び化合物 |
JP7354986B2 (ja) * | 2019-11-20 | 2023-10-03 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP7494716B2 (ja) * | 2020-01-22 | 2024-06-04 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP2022077982A (ja) * | 2020-11-12 | 2022-05-24 | 住友化学株式会社 | 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
JP2022091525A (ja) * | 2020-12-09 | 2022-06-21 | 東京応化工業株式会社 | レジスト組成物及びレジストパターン形成方法 |
JP2022091527A (ja) * | 2020-12-09 | 2022-06-21 | 東京応化工業株式会社 | レジスト組成物及びレジストパターン形成方法 |
US20230400768A1 (en) * | 2020-12-17 | 2023-12-14 | Jsr Corporation | Radiation-sensitive composition and method of forming resist pattern |
JPWO2022138044A1 (zh) * | 2020-12-25 | 2022-06-30 | ||
KR20230129375A (ko) * | 2021-01-08 | 2023-09-08 | 제이에스알 가부시끼가이샤 | 감방사선성 조성물 및 레지스트 패턴 형성 방법 |
WO2023162565A1 (ja) * | 2022-02-25 | 2023-08-31 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、及び電子デバイスの製造方法 |
JP7446352B2 (ja) * | 2022-03-15 | 2024-03-08 | 東京応化工業株式会社 | レジスト組成物、レジストパターン形成方法、化合物、及び、酸発生剤 |
JP2023177038A (ja) * | 2022-06-01 | 2023-12-13 | 信越化学工業株式会社 | 化学増幅ポジ型レジスト組成物及びレジストパターン形成方法 |
JP2023177048A (ja) * | 2022-06-01 | 2023-12-13 | 信越化学工業株式会社 | 化学増幅ネガ型レジスト組成物及びレジストパターン形成方法 |
WO2024029354A1 (ja) * | 2022-08-01 | 2024-02-08 | サンアプロ株式会社 | スルホニウム塩、及び前記スルホニウム塩を含む酸発生剤 |
JP2024062389A (ja) | 2022-10-24 | 2024-05-09 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4288446B2 (ja) * | 2000-10-23 | 2009-07-01 | 信越化学工業株式会社 | 新規オニウム塩及びレジスト材料用光酸発生剤並びにレジスト材料及びパターン形成方法 |
JP4288445B2 (ja) * | 2000-10-23 | 2009-07-01 | 信越化学工業株式会社 | 新規オニウム塩及びレジスト材料用光酸発生剤並びにレジスト材料及びパターン形成方法 |
TWI246525B (en) * | 2001-11-06 | 2006-01-01 | Wako Pure Chem Ind Ltd | Hybrid onium salt |
US7297616B2 (en) * | 2003-04-09 | 2007-11-20 | Rohm And Haas Electronic Materials Llc | Methods, photoresists and substrates for ion-implant lithography |
JP4858714B2 (ja) * | 2006-10-04 | 2012-01-18 | 信越化学工業株式会社 | 高分子化合物、レジスト材料、及びパターン形成方法 |
JP4849267B2 (ja) * | 2006-10-17 | 2012-01-11 | 信越化学工業株式会社 | レジスト材料及びこれを用いたパターン形成方法 |
JP2008163056A (ja) * | 2006-12-26 | 2008-07-17 | Lion Corp | ハイパーブランチポリマーの合成方法、ハイパーブランチポリマー、レジスト組成物、半導体集積回路、および半導体集積回路の製造方法 |
US7858287B2 (en) * | 2007-11-30 | 2010-12-28 | Hyogo Prefecture | Photosensitive resin, and photosensitive composition |
KR100998503B1 (ko) * | 2008-10-30 | 2010-12-07 | 금호석유화학 주식회사 | 방향족 환을 포함하는 산 발생제 |
JP5460230B2 (ja) * | 2008-10-31 | 2014-04-02 | 富士フイルム株式会社 | ポジ型感光性組成物 |
KR20110132206A (ko) * | 2010-06-01 | 2011-12-07 | 금호석유화학 주식회사 | 광산발생제, 이의 제조방법 및 이를 포함하는 레지스트 조성물 |
JP5622448B2 (ja) * | 2010-06-15 | 2014-11-12 | 東京応化工業株式会社 | レジスト組成物、レジストパターン形成方法、高分子化合物、化合物 |
JP5740322B2 (ja) * | 2012-02-06 | 2015-06-24 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、それを用いた感活性光線性又は感放射線性膜及びパターン形成方法、半導体デバイスの製造方法及び半導体デバイス、並びに、化合物 |
JP6028716B2 (ja) * | 2013-11-05 | 2016-11-16 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP6248882B2 (ja) * | 2014-09-25 | 2017-12-20 | 信越化学工業株式会社 | スルホニウム塩、レジスト組成物及びレジストパターン形成方法 |
JP6544248B2 (ja) * | 2015-02-09 | 2019-07-17 | 信越化学工業株式会社 | レジスト材料及びこれを用いたパターン形成方法 |
JP6531684B2 (ja) * | 2015-04-13 | 2019-06-19 | 信越化学工業株式会社 | 新規オニウム塩化合物を用いた化学増幅型ネガ型レジスト組成物及びレジストパターン形成方法 |
-
2017
- 2017-03-22 JP JP2017055799A patent/JP6648726B2/ja active Active
-
2018
- 2018-03-14 US US15/920,641 patent/US10613436B2/en active Active
- 2018-03-19 TW TW107109207A patent/TWI664162B/zh active
- 2018-03-20 KR KR1020180031830A patent/KR102078914B1/ko active IP Right Grant
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI720792B (zh) * | 2019-01-25 | 2021-03-01 | 日商信越化學工業股份有限公司 | 光阻材料及圖案形成方法 |
TWI747201B (zh) * | 2019-03-22 | 2021-11-21 | 日商信越化學工業股份有限公司 | 光阻組成物及圖案形成方法 |
US11579526B2 (en) | 2019-03-22 | 2023-02-14 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
TWI781661B (zh) * | 2020-06-25 | 2022-10-21 | 日商信越化學工業股份有限公司 | 阻劑材料及圖案形成方法 |
Also Published As
Publication number | Publication date |
---|---|
JP6648726B2 (ja) | 2020-02-14 |
KR102078914B1 (ko) | 2020-02-19 |
US20180275512A1 (en) | 2018-09-27 |
TWI664162B (zh) | 2019-07-01 |
JP2018159744A (ja) | 2018-10-11 |
US10613436B2 (en) | 2020-04-07 |
KR20180107738A (ko) | 2018-10-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI664162B (zh) | 光阻材料及圖案形成方法 | |
TWI635073B (zh) | 光阻材料及圖案形成方法 | |
TWI633080B (zh) | 光阻材料及圖案形成方法 | |
TWI641908B (zh) | 光阻材料及圖案形成方法 | |
TWI672288B (zh) | 光阻材料及圖案形成方法 | |
TWI664496B (zh) | 光阻材料及圖案形成方法 | |
TWI647533B (zh) | 光阻材料及圖案形成方法 | |
TWI649617B (zh) | 光阻材料及圖案形成方法 | |
TWI611262B (zh) | 光阻材料及圖案形成方法 | |
TWI682243B (zh) | 光阻材料及圖案形成方法 | |
TWI523836B (zh) | 光阻材料及圖案形成方法 | |
TW201904940A (zh) | 光阻材料及圖案形成方法 | |
TWI637971B (zh) | 光阻材料及圖案形成方法 | |
TW201823333A (zh) | 光阻材料及圖案形成方法 | |
TW202014800A (zh) | 光阻材料及圖案形成方法 | |
TWI611259B (zh) | 光阻材料及圖案形成方法 | |
TW201923455A (zh) | 光阻材料及圖案形成方法 | |
TWI647536B (zh) | 光阻材料及圖案形成方法 | |
TWI612038B (zh) | 光阻材料及圖案形成方法 | |
TWI666225B (zh) | 光阻材料及圖案形成方法 | |
TWI617537B (zh) | 光阻材料及圖案形成方法 | |
TW201923454A (zh) | 光阻材料及圖案形成方法 |