WO2018016615A1 - 化合物、樹脂、組成物並びにレジストパターン形成方法及び回路パターン形成方法 - Google Patents
化合物、樹脂、組成物並びにレジストパターン形成方法及び回路パターン形成方法 Download PDFInfo
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- WO2018016615A1 WO2018016615A1 PCT/JP2017/026423 JP2017026423W WO2018016615A1 WO 2018016615 A1 WO2018016615 A1 WO 2018016615A1 JP 2017026423 W JP2017026423 W JP 2017026423W WO 2018016615 A1 WO2018016615 A1 WO 2018016615A1
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- 0 CCC=C[C@@](C)(*)C=C[C@@](C)(*[C@]1(C)/C=C/[C@@]2(C)C=C[C@](C)(*)C=C1)C=CCC2(CC(C1*)C2(CC(C=CC)=C/C=C3)C1=C)C3=C2C(C)=C Chemical compound CCC=C[C@@](C)(*)C=C[C@@](C)(*[C@]1(C)/C=C/[C@@]2(C)C=C[C@](C)(*)C=C1)C=CCC2(CC(C1*)C2(CC(C=CC)=C/C=C3)C1=C)C3=C2C(C)=C 0.000 description 68
- GIZJZVCCBPLINI-UHFFFAOYSA-N CC(c(cc1)ccc1-c1ccccc1)(c(c(cccc1)c1cc1)c1OCCOCC1OC1)c1c(cccc2)c2ccc1OCCOCC1OC1 Chemical compound CC(c(cc1)ccc1-c1ccccc1)(c(c(cccc1)c1cc1)c1OCCOCC1OC1)c1c(cccc2)c2ccc1OCCOCC1OC1 GIZJZVCCBPLINI-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
- C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
Definitions
- the present invention relates to a compound having a specific structure, a resin, and a composition containing these.
- the present invention also relates to a pattern forming method (resist pattern forming method and circuit pattern forming method) using the composition.
- the molecular weight is as large as about 10,000 to 100,000, and the molecular weight distribution is wide, resulting in roughness on the pattern surface, making it difficult to control the pattern size, and limiting the miniaturization.
- various low molecular weight resist materials have been proposed so far in order to provide resist patterns with higher resolution. Since the low molecular weight resist material has a small molecular size, it is expected to provide a resist pattern with high resolution and low roughness.
- an alkali development negative radiation-sensitive composition for example, see Patent Document 1 and Patent Document 2 below
- a low molecular weight polynuclear polyphenol compound as a main component
- a low molecular weight resist having high heat resistance As a candidate for the material, an alkali developing negative radiation-sensitive composition (for example, see Patent Document 3 and Non-Patent Document 1 below) using a low molecular weight cyclic polyphenol compound as a main component has also been proposed.
- polyphenol compounds are known to be able to impart high heat resistance while having a low molecular weight, and are useful for improving the resolution and roughness of resist patterns (for example, the following non-patent documents) 2).
- the present inventors have excellent etching resistance, and are resist compositions containing a compound having a specific structure and an organic solvent as a material that is soluble in a solvent and applicable to a wet process (for example, see Patent Document 4 below). ).
- a material for forming an underlayer film for a multilayer resist process has been proposed that contains at least a resin component having a substituent that generates a sulfonic acid residue and a solvent (see, for example, Patent Document 5 below).
- resist underlayer film materials containing a polymer having a specific repeating unit have been proposed as a material for realizing a resist underlayer film for lithography having a lower dry etching rate selectivity than resist (for example, the following patents) Reference 6). Furthermore, in order to realize a resist underlayer film for lithography having a low dry etching rate selection ratio compared with a semiconductor substrate, a repeating unit of acenaphthylenes and a repeating unit having a substituted or unsubstituted hydroxy group are copolymerized. A resist underlayer film material containing a polymer is proposed (see, for example, Patent Document 7 below).
- an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas or the like as a raw material is well known.
- a resist underlayer film material capable of forming a resist underlayer film by a wet process such as spin coating or screen printing is required.
- the present inventors have a composition for forming an underlayer film for lithography containing a compound having a specific structure and an organic solvent as a material having excellent etching resistance, high heat resistance, soluble in a solvent and applicable to a wet process.
- the thing (for example, refer the following patent document 8) is proposed.
- a silicon nitride film formation method for example, see Patent Document 9 below
- a silicon nitride film CVD formation method for example, And the following Patent Document 10.
- an intermediate layer material for a three-layer process a material containing a silsesquioxane-based silicon compound is known (see, for example, Patent Documents 11 and 12 below).
- optical component forming compositions have been proposed.
- examples thereof include acrylic resins (see, for example, Patent Documents 13 to 14 below).
- a polyphenol having a specific structure derived from an alcohol group or an epoxy group has also been proposed (see, for example, Patent Document 15 below).
- the present invention has been made in view of the above-described problems, and the object thereof is a compound and resin having high solubility in a safe solvent, good heat resistance and etching resistance, a composition using the same, and The present invention relates to a resist pattern forming method and a circuit pattern forming method using the composition.
- the present inventors have found that the above problems can be solved by using a compound or resin having a specific structure, and have completed the present invention. That is, the present invention is as follows.
- a compound represented by the following formula (0) (In the formula (0), R Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, R Z is an N-valent group having 1 to 60 carbon atoms or a single bond, R T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent.
- the hydrogen atom is a group substituted with a hydroxyalkyl group or a glycidyl group
- the alkyl group, the aryl group, the alkenyl group, and the alkoxy group include an ether bond, a ketone bond, or an ester bond.
- At least one of RT includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, X represents an oxygen atom, a sulfur atom or no bridge, m is each independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9, N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas in N [] may be the same or different, Each r is independently an integer of 0-2. ) ⁇ 2> The compound according to ⁇ 1>, wherein the compound represented by the formula (0) is a compound represented by the following formula (1).
- R 0 has the same meaning as R Y
- R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond
- R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
- a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
- R 2 to R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
- m 2 and m 3 are each independently an integer of 0 to 8
- m 4 and m 5 are each independently an integer of 0 to 9
- m 2 , m 3 , m 4 and m 5 are not 0 simultaneously
- n is synonymous with the above N, and here, when n is an integer of 2 or more, the structural formulas in the n [] may be the same or different
- p 2 to p 5 have the same meaning as r.
- the hydrogen atom is a group substituted with a hydroxyalkyl group or a glycidyl group
- the alkyl group, the aryl group, the alkenyl group, and the alkoxy group include an ether bond, a ketone bond, or an ester bond.
- R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
- n A has the same meaning as N above.
- n A is an integer of 2 or more
- the structural formulas in n A [] may be the same or different
- X A is synonymous with X
- m 2A is each independently an integer of 0 to 7, provided that at least one m 2A is an integer of 1 to 7;
- q A is each independently 0 or 1.
- R 0 , R 1 , R 4 , R 5 , n, p 2 to p 5 , m 4 and m 5 are as defined above.
- R 6 to R 7 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
- An alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group, which may have R 10 to R 11 are each independently a hydrogen atom or a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group,
- at least one of R 10 to R 11 is one group selected from a hydroxyalkyl group, a glycidyloxyalkyl group, or a glycidyl group
- m 6 and m 7 are each independently an integer of 0 to 7, However, m 4 , m 5 , m 6 and m 7 are not 0 at the same time.
- Each R 4A is independently a hydrogen atom or a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group;
- at least one of R 4A is a hydroxyalkyl group, a glycidyloxyalkyl group, or a glycidyl group
- m 6A is each independently an integer of 0 to 5.
- the resin according to ⁇ 7> which has a structure represented by the following formula (3).
- L is an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, or an optionally substituted carbon number.
- R 0 has the same meaning as R Y
- R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond
- R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
- a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
- n is synonymous with the above N, and here, when n is an integer of 2 or more, the structural formulas in the n [] may be the same or different, p 2 to p 5 have the same meaning as r.
- L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent.
- the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond
- R 0A has the same meaning as R Y
- R 1A is an n A valent group having 1 to 30 carbon atoms or a single bond
- R 2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
- the hydrogen atom is a group substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
- the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether bonds, ketone bonds Or an ester bond
- at least one of R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
- n A has the same meaning as N above.
- n A is an integer of 2 or more
- the structural formulas in n A [] may be the same or different
- X A is synonymous with X
- m 2A is each independently an integer of 0 to 7, provided that at least one m 2A is an integer of 1 to 6
- q A is each independently 0 or 1.
- ⁇ 10> Contains one or more selected from the group consisting of the compound according to any one of ⁇ 1> to ⁇ 6> and the resin according to any one of ⁇ 7> to ⁇ 9>.
- Composition. ⁇ 11> The composition according to ⁇ 10>, further including a solvent.
- ⁇ 12> The composition according to ⁇ 10> or ⁇ 11>, further including an acid generator.
- the crosslinking agent is at least one selected from the group consisting of phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, and azide compounds.
- the content of the cross-linking agent is selected from the group consisting of the compound according to any one of the above ⁇ 1> to ⁇ 6> and the resin according to any one of the above ⁇ 7> to ⁇ 9>.
- the composition according to any one of ⁇ 13> to ⁇ 15> which is 0.1 to 100 parts by mass with respect to 100 parts by mass of the total mass of the composition containing one or more selected.
- ⁇ 17> The composition according to any one of ⁇ 13> to ⁇ 16>, further including a crosslinking accelerator.
- the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.
- ⁇ 19> The group consisting of the compound according to any one of ⁇ 1> to ⁇ 6> and the resin according to any one of ⁇ 7> to ⁇ 9>, wherein the content of the crosslinking accelerator is The composition according to ⁇ 17> or ⁇ 18>, which is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total mass of the composition containing one or more selected from the above.
- ⁇ 20> The composition according to any one of ⁇ 10> to ⁇ 19>, further comprising a radical polymerization initiator.
- ⁇ 21> The ⁇ 10> to ⁇ 20, wherein the radical polymerization initiator is at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator.
- the content of the radical polymerization initiator includes the compound according to any one of ⁇ 1> to ⁇ 6> and the resin according to any one of ⁇ 7> to ⁇ 9>.
- the composition according to any one of the above ⁇ 10> to ⁇ 21> which is 0.05 to 25 parts by mass with respect to 100 parts by mass of the total mass of the composition containing one or more selected from the group.
- composition according to any one of ⁇ 10> to ⁇ 22> which is used for forming a film for lithography.
- ⁇ 24> The composition according to any one of ⁇ 10> to ⁇ 22>, which is used for forming a resist permanent film.
- ⁇ 25> The composition according to any one of ⁇ 10> to ⁇ 22>, which is used for forming an optical component.
- a resist pattern including a step of forming a photoresist layer on the substrate by using the composition according to the above ⁇ 23>, irradiating a predetermined region of the photoresist layer with radiation, and performing development. Forming method.
- a lower layer film is formed on the substrate using the composition according to the above ⁇ 23>, and at least one photoresist layer is formed on the lower layer film, and then a predetermined layer of the photoresist layer is formed.
- a resist pattern forming method including a step of irradiating a region with radiation and performing development.
- a lower layer film is formed on the substrate using the composition described in ⁇ 23>, an intermediate layer film is formed on the lower layer film using a resist intermediate layer film material, and the intermediate layer film is formed.
- a circuit pattern including a step of forming a pattern on the substrate by etching the substrate using the obtained intermediate layer film pattern as an etching mask and etching the substrate using the obtained lower layer film pattern as an etching mask Forming method.
- a compound and a resin having high solubility in a safe solvent and good heat resistance and etching resistance, a composition using the same, and a resist pattern forming method and circuit pattern forming using the composition A method can be provided.
- the compound of this embodiment is a compound represented by the formula (0) described later, or a resin obtained using the compound as a monomer.
- the compound and resin of this embodiment can be applied to a wet process, and is useful for forming a photoresist and an underlayer film for photoresist excellent in heat resistance, solubility in a safe solvent, and etching resistance. It can be used for a composition useful for formation, a pattern formation method using the composition, and the like.
- the compound and resin of the present embodiment are excellent in sensitivity and resolution when used in a photosensitive material, and while maintaining high heat resistance, further, general-purpose organic solvents, other compounds, and resin components , And a resist permanent film having excellent compatibility with the additive.
- the above-described composition uses a compound or resin having a specific structure that has high heat resistance and high solvent solubility, so that deterioration of the film during high-temperature baking is suppressed, and etching resistance against oxygen plasma etching and the like is also improved. An excellent resist and lower layer film can be formed.
- the adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed.
- the above-described composition has a high refractive index and coloration is suppressed by a wide range of heat treatment from low temperature to high temperature, it is useful as various optical forming compositions.
- the compound of this embodiment is represented by the following formula (0).
- (0) (In the formula (0), R Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, R Z is an N-valent group having 1 to 60 carbon atoms or a single bond, R T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent.
- the hydrogen atom is a group substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
- the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether bonds, ketone bonds
- at least one of R T includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
- X represents an oxygen atom, a sulfur atom or no bridge
- m is each independently an integer of 0 to 9, wherein at least one of m is an integer of
- R Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
- the alkyl group a linear, branched or cyclic alkyl group can be used. Since R Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, the heat resistance is relatively high and the solvent solubility is improved.
- R Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, the oxidative decomposition of the compound is further suppressed, coloring is suppressed, and heat resistance is improved. From the viewpoint of improving the solubility of the solvent and the solvent.
- R z is an N-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded through this R z .
- N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas in N [] may be the same or different.
- N-valent group examples include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group.
- the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.
- the N-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.
- R T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent.
- the hydrogen atom is a group substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
- the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether bonds, ketone bonds Or it may contain an ester bond.
- RT includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- the alkyl group, alkenyl group and alkoxy group may be a linear, branched or cyclic group.
- a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group in which a glycidyl group is substituted means a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group, and a hydrogen atom of the hydroxyl group.
- a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group and a hydroxyl group (hydroxy group) of the hydroxyalkyl group is substituted with another substituent is also included.
- the group in which the hydroxyl group of the hydroxyalkyl group is substituted with another substituent is not particularly limited, and examples thereof include a glycidyloxyalkyl group in which the hydroxyl group is substituted with a glycidyl group.
- the alkyl group in the hydroxyalkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a propyl group.
- the hydroxyalkyl group and glycidyl group may be substituted with a hydrogen atom of a hydroxyl group through another linking group.
- the other linking group include an oxygen atom, an alkylene group, and an oxyalkylene group.
- X represents an oxygen atom, a sulfur atom or no bridge. When X is an oxygen atom or a sulfur atom, it tends to develop high heat resistance, and is preferably an oxygen atom. X is preferably non-crosslinked from the viewpoint of solubility.
- M is each independently an integer of 0 to 9, and at least one of m is an integer of 1 to 9.
- Each r is independently an integer of 0-2.
- the numerical range of m described above is determined according to the ring structure determined by r.
- the compound represented by the formula (0) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. Moreover, it has a quaternary carbon in the molecule, the crystallinity is suppressed, and it is suitably used as a film-forming composition for lithography that can be used for manufacturing a film for lithography.
- the compound represented by the formula (0) has high solubility in a safe solvent, and has good heat resistance and etching resistance, and the resist forming composition for lithography according to this embodiment gives a good resist pattern shape. .
- the compound represented by the formula (0) has a relatively low molecular weight and a low viscosity, even if the substrate has a step (particularly, a fine space or a hole pattern), the step It is easy to improve the flatness of the film while uniformly filling every corner, and as a result, the underlayer film forming composition for lithography using the same can have relatively advantageous enhancement of embedding and planarization characteristics. . Moreover, since it is a compound having a relatively high carbon concentration, high etching resistance is also imparted.
- the compound represented by the formula (0) has a high aromatic density and a high refractive index, and is also useful as a composition for forming various optical parts because coloration is suppressed by a wide range of heat treatment from low to high temperatures. It is.
- the compound represented by the formula (0) preferably has a quaternary carbon from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloring, high heat resistance, and improving solvent solubility.
- Optical parts are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms It is useful as an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.
- R 0 has the same meaning as R Y
- R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond
- R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
- a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
- R 2 to R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
- m 2 and m 3 are each independently an integer of 0 to 8
- m 4 and m 5 are each independently an integer of 0 to 9
- m 2 , m 3 , m 4 and m 5 are not 0 simultaneously
- n is synonymous with the above N, and here, when n is an integer of 2 or more, the structural formulas in the n [] may be the same or different
- p 2 to p 5 have the same meaning as r.
- R 0 has the same meaning as R Y described above.
- R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded through R 1 .
- n is synonymous with N, and when n is an integer of 2 or more, the structural formulas in n [] may be the same or different.
- n-valent group examples include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group.
- the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.
- the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.
- R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
- a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
- R 2 to R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group in which a glycidyl group is substituted.
- the alkyl group, alkenyl group and alkoxy group may be a linear, branched or cyclic group.
- n 2 and m 3 are each independently an integer of 0 to 8
- m 4 and m 5 are each independently an integer of 0 to 9.
- m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
- p 2 to p 5 are each independently synonymous with r.
- the compound represented by the formula (1) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. Moreover, it has a quaternary carbon in the molecule, the crystallinity is suppressed, and it is suitably used as a film-forming composition for lithography that can be used for manufacturing a film for lithography.
- the solubility in a safe solvent is high, the heat resistance and the etching resistance are good, and the resist forming composition for lithography according to this embodiment gives a good resist pattern shape.
- the film has a relatively low molecular weight and low viscosity, even a substrate having a step (particularly, a fine space or a hole pattern) can be uniformly filled to every corner of the step and the film can be flattened.
- the composition for forming an underlayer film for lithography using the same can be relatively advantageously enhanced in embedding and planarization characteristics.
- it is a compound having a relatively high carbon concentration, high etching resistance is also imparted.
- the compound represented by the formula (1) has a high aromatic density, the refractive index is high, and the coloration is suppressed by a wide range of heat treatment from low temperature to high temperature, so that it is also useful as a composition for forming various optical components. is there.
- the one having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the present compound to suppress coloring, high heat resistance, and improving solvent solubility.
- Optical parts are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms It is useful as an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.
- the compound represented by the formula (1) is preferably a compound represented by the following formula (1-1) from the viewpoint of easy crosslinking and solubility in an organic solvent. (1-1)
- R 0 , R 1 , R 4 , R 5 , n, p 2 to p 5 , m 4 and m 5 are as defined above, and R 6 to R 7 are each independently A linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent.
- R 10 ⁇ R 11 are each independently a hydrogen atom or a hydroxy An alkyl group, a glycidyloxyalkyl group or a glycidyl group;
- at least one of R 10 to R 11 is a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group
- m 6 and m 7 are each independently an integer of 0 to 7.
- m 4 , m 5 , m 6 and m 7 are not 0 at the same time.
- the compound represented by the formula (1-1) is preferably a compound represented by the following formula (1-2) from the viewpoint of further crosslinkability and solubility in an organic solvent.
- R 0 , R 1 , R 6 , R 7 , R 10 , R 11 , n, p 2 to p 5 , m 6 and m 7 are as defined above, and R 8 to R 9 has the same meaning as R 6 to R 7 , and R 12 to R 13 have the same meaning as R 10 to R 11 .
- m 8 and m 9 are each independently an integer of 0 to 8. However, m 6 , m 7 , m 8 and m 9 are not 0 at the same time.
- the compound represented by the formula (1-2) is preferably a compound represented by the following formula (1a).
- R 0 to R 5 , m 2 to m 5 and n have the same meaning as described in the formula (1).
- the compound represented by the formula (1a) is more preferably a compound represented by the following formula (1b) from the viewpoint of solubility in an organic solvent.
- R 0 , R 1 , R 4 , R 5 , R 10 , R 11 , m 4 , m 5 , and n are as defined in the formula (1), and R 6 , R 7 , R 10 , R 11 , m 6 and m 7 have the same meanings as described in the formula (1-1).
- the compound represented by the formula (1a) is more preferably a compound represented by the following formula (1b ′) from the viewpoint of reactivity. (1b ')
- R 0 , R 1 , R 4 , R 5 , R 10 , R 11 , m 4 , m 5 , and n are as defined in the formula (1), and R 6 , R 7 , R 10 , R 11 , m 6 and m 7 have the same meanings as described in the formula (1-1).
- the compound represented by the formula (1b) is more preferably a compound represented by the following formula (1c) from the viewpoint of solubility in an organic solvent.
- R 0 , R 1 , R 6 to R 13 , m 6 to m 9 , and n are as defined in the formula (1-2).
- the compound represented by the formula (1b ′) is more preferably a compound represented by the following formula (1c ′) from the viewpoint of reactivity.
- R 0 , R 1 , R 6 to R 13 , m 6 to m 9 , and n are as defined in the formula (1-2).
- X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
- X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
- X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
- X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
- X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
- X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
- X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
- X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
- X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
- OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those described in, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is synonymous with what was demonstrated by the said Formula (0).
- R Z ' are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is synonymous with what was demonstrated by the said Formula (0).
- R Z ' are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is synonymous with what was demonstrated by the said Formula (0).
- R Z ' are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is synonymous with what was demonstrated by the said Formula (0).
- R Z ' are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is synonymous with what was demonstrated by the said Formula (0).
- R Z ' are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
- at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- R 2 , R 3 , R 4 , and R 5 have the same meaning as described in the formula (1).
- m 2 and m 3 are integers from 0 to 6
- m 4 and m 5 are integers from 0 to 7.
- at least one selected from R 2 , R 3 , R 4 and R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
- R 2 , R 3 , R 4 , and R 5 have the same meaning as described in the formula (1).
- m 2 and m 3 are integers from 0 to 6
- m 4 and m 5 are integers from 0 to 7.
- at least one selected from R 2 , R 3 , R 4 and R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
- R 2 , R 3 , R 4 , and R 5 have the same meaning as described in the formula (1).
- m 2 and m 3 are integers from 0 to 6
- m 4 and m 5 are integers from 0 to 7.
- at least one selected from R 2 , R 3 , R 4 and R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
- R 2 , R 3 , R 4 , and R 5 have the same meaning as described in the formula (1).
- m 2 and m 3 are integers from 0 to 6
- m 4 and m 5 are integers from 0 to 7.
- at least one selected from R 2 , R 3 , R 4 and R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
- R 10 , R 11 , R 12 , R 13 have the same meanings as described in the formula (1-2), and R 10 to R 13 are each independently a hydrogen atom. Or a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group, and at least one of R 10 to R 11 is one group selected from a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group.
- the compound represented by the formula (1) is particularly preferably a compound represented by the following formulas (BiF-1) to (BiF-5) from the viewpoint of further solubility in an organic solvent (specific examples) R 10 to R 13 therein are as defined above).
- R 0 , R 1 and n are as defined in the formula (1-1), and R 10 ′ and R 11 ′ are R 10 and R described in the formula (1-1).
- 11 and R 4 ′ and R 5 ′ each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 6 carbon atoms which may have a substituent.
- aryl groups an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, A carboxylic acid group, a thiol group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are Ether bond, ketone bond or ester bond May also comprise, group or at least one of the hydrogen atoms of the hydroxyl group substituted with a hydroxyl group of R 10 'and R 11' includes a group substituted with a glycidyl group, m 4 'and m 5' is , 0 to 8, m 10 ′ and m 11 ′ are integers
- R 0 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, phenyl group, naphthyl group , Anthracene group, pyrenyl group, biphenyl group and heptacene group.
- R 4 ′ and R 5 ′ are, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group , Naphthyl group, anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group
- R 0 , R 4 ′ and R 5 ′ includes an isomer.
- the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- R 10 to R 13 have the same meanings as described in the formula (1-2),
- R 16 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, carbon number A bivalent aryl group having 6 to 30 carbon atoms or a divalent alkenyl group having 2 to 30 carbon atoms.
- R 16 is, for example, a methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triacontene group, cyclopropene group, Cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriacontene group, divalent norbornyl group, divalent adamantyl group, divalent Phenyl group, divalent naphthyl group, divalent anthracene group, divalent pyrene group, divalent biphenyl group, divalent heptacene group, divalent
- R 10 to R 13 have the same meanings as described in the above formula (1-2), and R 14 each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms.
- m 14 ′ is an integer from 0 to 4, and m 14 is an integer from 0 to 5.
- R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
- R 14 includes an isomer.
- the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a
- R 0 , R 4 ′ , R 5 ′ , m 4 ′ , m 5 ′ , m 10 ′ and m 11 ′ are as defined above, and R 1 ′ is a group having 1 to 60 carbon atoms. is there.
- R 10 to R 13 have the same meanings as described in the above formula (1-2), and R 14 each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms.
- m 14 is an integer of 0 to 5
- 14 ′ is an integer from 0 to 4
- m 14 ′′ is an integer from 0 to 3.
- R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
- R 14 includes an isomer.
- the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a
- R 10 to R 13 have the same meanings as described in the formula (1-2),
- R 15 represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.
- R 15 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
- R 15 includes an isomer.
- the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a
- R 10 to R 13 have the same meanings as described in the formula (1-2). From the viewpoint of availability of raw materials, the following compounds are more preferable.
- R 10 to R 13 have the same meanings as described in the formula (1-2).
- the compound represented by the formula (0) preferably has the following structure from the viewpoint of etching resistance.
- R 0A has the same meaning as the formula R Y
- R 1A ′ has the same meaning as R Z
- R 10 to R 13 have the same meaning as described in the formula (1-2).
- R 0A has the same meaning as the formula R Y
- R 1A ′ has the same meaning as R Z
- R 10 to R 13 have the same meaning as described in the formula (1-2).
- R 14 each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, or 1 to 30 carbon atoms.
- An alkoxy group, a halogen atom, and a thiol group, and m 14 ′ is an integer of 0 to 4.
- R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
- R 14 includes an isomer.
- the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- R 10 to R 13 have the same meanings as described in the formula (1-2),
- R 15 represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.
- R 15 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
- R 15 includes an isomer.
- the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- R 10 to R 13 have the same meanings as described in the formula (1-2),
- R 16 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, carbon number A bivalent aryl group having 6 to 30 carbon atoms or a divalent alkenyl group having 2 to 30 carbon atoms.
- R 16 is, for example, a methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triacontene group, cyclopropene group, Cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriacontene group, divalent norbornyl group, divalent adamantyl group, divalent Examples thereof include a phenyl group, a divalent naphthyl group, a divalent anthracene group, a divalent heptacene group, a divalent vinyl group,
- R 10 ⁇ R 13 have the same meanings as those described by the formula (1-2)
- R 14 are each independently C 1 -C 30 linear, alkyl branched or cyclic Group, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group
- m 14 ′ is an integer of 0 to 4.
- R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
- R 14 includes an isomer.
- the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- R 10 to R 13 have the same meanings as described in the formula (1-2), and each R 14 is independently a linear or branched group having 1 to 30 carbon atoms. Or a cyclic alkyl group, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, or a thiol group, and m 14 is an integer of 0 to 5 It is.
- R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
- R 14 includes an isomer.
- the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- R 10 to R 13 have the same meanings as described in the formula (1-2).
- compounds having a dibenzoxanthene skeleton are more preferable from the viewpoint of heat resistance.
- the compound represented by the formula (0) is more preferably a compound listed below from the viewpoint of availability of raw materials.
- R 10 to R 13 have the same meanings as described in the formula (1-2).
- the compounds listed above are preferably compounds having a dibenzoxanthene skeleton from the viewpoint of heat resistance.
- the compound represented by the formula (0) preferably has the following structure from the viewpoint of raw material availability.
- R 0A has the same meaning as the formula R Y
- R 1A ′ has the same meaning as R Z
- R 10 to R 13 have the same meaning as described in the formula (1-2).
- the compounds listed above are preferably compounds having a xanthene skeleton from the viewpoint of heat resistance.
- R 10 to R 13 have the same meanings as described in formula (1-2), and R 14 , R 15 , R 16 , m 14 and m 14 ′ have the same meanings as described above.
- the compound represented by the formula (0) used in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited.
- the compound represented by formula (1) as an example, the compound represented by formula (0) can be synthesized as follows.
- the compound represented by the formula (1) is obtained by polycondensation reaction of biphenols, binaphthols or bianthracenols with the corresponding ketones under an acid catalyst under normal pressure to obtain a polyphenol compound, Subsequently, it is obtained by introducing a hydroxyalkyl group or a glycidyl group into at least one phenolic hydroxyl group of the polyphenol compound, or further introducing a glycidyl group into the hydroxy group of the hydroxyalkyl group.
- combination can also be performed under pressure as needed.
- transduces a hydroxyalkyl group or a glycidyl group not only after the condensation reaction of binaphthol etc. and ketones, but the stage before a condensation reaction may be sufficient.
- the timing of introducing the glycidyl group into the hydroxy group of the hydroxyalkyl group may be any stage after the introduction of the hydroxyalkyl group.
- biphenols examples include, but are not limited to, biphenol, methyl biphenol, methoxy binaphthol, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is more preferable to use biphenol from the viewpoint of stable supply of raw materials.
- binaphthols examples include, but are not limited to, binaphthol, methyl binaphthol, methoxy binaphthol, and the like. These can be used alone or in combination of two or more. Among these, it is more preferable to use binaphthol in terms of increasing the carbon atom concentration and improving heat resistance.
- bianthraceneols examples include, but are not particularly limited to, bianthraceneol, methylbianthracenol, methoxybianthracenol, and the like. These can be used alone or in combination of two or more. Among these, it is more preferable to use bianthraceneol in terms of increasing the carbon atom concentration and improving heat resistance.
- ketones examples include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene.
- Triacetylbenzene Triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. Is particularly limited to There. These can be used alone or in combination of two or more.
- the acid catalyst used in the reaction can be appropriately selected from known ones and is not particularly limited.
- inorganic acids and organic acids are widely known.
- inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, and succinic acid.
- Adipic acid sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid Organic acids such as naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Although it is mentioned, it is not specifically limited to these.
- an organic acid and a solid acid are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as availability and ease of handling.
- an acid catalyst 1 type can be used individually or in combination of 2 or more types.
- the amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst to be used, and further the reaction conditions, and is not particularly limited. It is preferable that it is a mass part.
- a reaction solvent may be used.
- the reaction solvent is not particularly limited as long as the reaction between the ketones to be used and biphenols, binaphthols, or bianthracenediol proceeds, and can be appropriately selected from known ones. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, or a mixed solvent thereof.
- a solvent can be used individually by 1 type or in combination of 2 or more types.
- the amount of these solvents used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that it is the range of these.
- the reaction temperature in the reaction can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C.
- the reaction temperature is preferably higher, and specifically in the range of 60 to 200 ° C.
- the reaction method can be appropriately selected from known methods, and is not particularly limited.
- the reaction method is a method in which biphenols, binaphthols or bianthracenediol, ketones, and a catalyst are charged all together, or biphenols and binaphthols.
- the obtained compound can be isolated according to a conventional method, and is not particularly limited.
- reaction conditions 1.0 mol to excess of biphenols, binaphthols or bianthracenediol and 0.001 to 1 mol of an acid catalyst are used with respect to 1 mol of ketones, and 50 to 50 at normal pressure.
- the reaction proceeds at 150 ° C. for about 20 minutes to 100 hours.
- the target product can be isolated by a known method.
- the reaction solution is concentrated, pure water is added to precipitate the reaction product, cooled to room temperature, filtered and separated, and the resulting solid is filtered and dried, followed by column chromatography.
- the compound represented by the above formula (1), which is the target product can be obtained by separating and purifying from the by-product, and performing solvent distillation, filtration and drying.
- a method of introducing a hydroxyalkyl group into at least one phenolic hydroxyl group of a polyphenol compound and introducing a hydroxyalkyl group or a glycidyl group into the hydroxy group is also known.
- a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of a polyphenol compound as follows.
- the hydroxyalkyl group may be introduced into the phenolic hydroxyl group via an oxyalkyl group.
- a hydroxyalkyloxyalkyl group or a hydroxyalkyloxyalkyloxyalkyl group is introduced.
- a compound for introducing a hydroxyalkyl group can be synthesized or easily obtained by a known method.
- chloroethanol bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide , Propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but are not particularly limited.
- a polyphenol compound and the compound for introducing the hydroxyalkyl group described above are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
- an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
- metal alkoxide sodium methoxide, sodium ethoxide, potassium methoxide, alkali metal such as potassium ethoxide or alkaline earth metal alkoxide
- metal hydroxide sodium hydroxide, alkali metal such as potassium hydroxide
- alkaline earth metal carbonate etc.
- alkali metal such as sodium hydrogen carbonate, potassium hydrogen carbonate, or alkaline earth hydrogen carbonate
- amines for example, tertiary amines (trialkylamines such as triethylamine, N, N -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), carboxylic acid metal salts (alkali metal acetates or alkaline earth metal salts such as sodium acetate, calcium acetate, etc.) ) 20-15 at atmospheric pressure in the presence of a base catalyst such as an organic base The reaction is allowed to proceed
- the reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness.
- the compound in which the hydrogen atom of the hydroxyl group is substituted with a hydroxyalkyl group can be obtained by washing with distilled water if necessary and drying.
- 2-chloroethyl acetate, 2-bromoethyl acetate, or 2-iodoethyl acetate is used, a hydroxyethyl group is introduced by deacylation after an acetoxyethyl group is introduced.
- ethylene carbonate, propylene carbonate, or butylene carbonate a hydroxyalkyl group is introduced by adding an alkylene carbonate to cause a decarboxylation reaction.
- a glycidyl group can be introduced into at least one phenolic hydroxyl group or hydroxyalkyl group of the polyphenol compound as follows.
- a method of introducing a glycidyl group into the phenolic hydroxyl group or hydroxyalkyl group is also known.
- a compound for introducing a glycidyl group can be synthesized or easily obtained by a known method, and examples thereof include epichlorohydrin and epibromohydrin, but are not particularly limited.
- a polyphenol compound and a compound for introducing the glycidyl group described above are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
- an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
- metal alkoxide sodium methoxide, sodium ethoxide, potassium methoxide, alkali metal such as potassium ethoxide or alkaline earth metal alkoxide
- metal hydroxide sodium hydroxide, alkali metal such as potassium hydroxide
- alkaline earth metal carbonate etc.
- alkali metal such as sodium hydrogen carbonate, potassium hydrogen carbonate, or alkaline earth hydrogen carbonate
- amines for example, tertiary amines (trialkylamines such as triethylamine, N, N -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), carboxylic acid metal salts (alkali metal acetates or alkaline earth metal salts such as sodium acetate, calcium acetate, etc.) ) 20-15 at atmospheric pressure in the presence of a base catalyst such as an organic base The reaction is allowed to proceed
- reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness. Accordingly, the compound in which the hydrogen atom of the phenolic hydroxyl group or hydroxyalkyl group is substituted with a glycidyl group can be obtained by washing with distilled water and drying.
- the group substituted with a hydroxyalkyl group or a glycidyl group reacts in the presence of a radical or an acid / alkali, and has solubility in an acid, an alkali, or an organic solvent used in a coating solvent or a developer.
- the group substituted with a hydroxyalkyl group or a glycidyl group has a property of causing a chain reaction in the presence of a radical or an acid / alkali in order to enable pattern formation with higher sensitivity and higher resolution. preferable.
- the compound represented by the formula (0) can be used as it is as a film-forming composition for lithography. Moreover, it can be used also as resin obtained by using the compound represented by the said Formula (0) as a monomer.
- the resin of this embodiment is a resin having a unit structure derived from the general formula (0).
- it can also be used as a resin obtained by reacting a compound represented by the formula (0) with a compound having crosslinking reactivity.
- the resin obtained using the compound represented by the formula (0) as a monomer include those having a structure represented by the following formula (3). That is, the composition of the present embodiment may contain a resin having a structure represented by the following formula (3).
- L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent.
- the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond
- R 0 has the same meaning as R Y
- R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond
- R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
- a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
- n is synonymous with the above N, and here, when n is an integer of 2 or more, the structural formulas in the n [] may be the same or different, p 2 to p 5 have the same meaning as r. )
- L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent. It may be an alkoxylene group having 1 to 30 carbon atoms or a single bond.
- the alkylene group, the arylene group, and the alkoxylene group may include an ether bond, a ketone bond, or an ester bond.
- the alkylene group and alkoxylene group may be a linear, branched or cyclic group.
- R 0 , R 1 , R 2 to R 5 , m 2 and m 3 , m 4 and m 5 , p 2 to p 5 , and n are as defined in the formula (1).
- m 2 , m 3 , m 4 and m 5 are not simultaneously 0, and at least one of R 2 to R 5 is substituted with a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a glycidyl group Group.
- the resin of the present embodiment can be obtained by reacting the compound represented by the formula (0) with a compound having crosslinking reactivity.
- a known compound can be used without particular limitation as long as the compound represented by the formula (0) can be oligomerized or polymerized. Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.
- the resin obtained using the compound represented by the formula (0) as a monomer include, for example, the compound represented by the formula (0) with an aldehyde and / or a ketone having a crosslinking reactivity.
- examples thereof include resins that have been novolakized by a condensation reaction or the like.
- aldehyde for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde
- examples thereof include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural.
- ketones include the aforementioned ketones. Among these, formaldehyde is more preferable. In addition, these aldehydes and / or ketones can be used individually by 1 type or in combination of 2 or more types.
- the amount of the aldehyde and / or ketone used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 moles relative to 1 mole of the compound represented by the formula (0). ⁇ 2 moles.
- a catalyst may be used.
- the acid catalyst used here can be appropriately selected from known ones and is not particularly limited.
- inorganic acids and organic acids are widely known.
- inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, and succinic acid.
- Adipic acid sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid Organic acids such as naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Although it is mentioned, it is not specifically limited to these.
- organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of production such as availability and ease of handling.
- hydrochloric acid or sulfuric acid is preferred from the viewpoint of production such as availability and ease of handling.
- 1 type can be used individually or in combination of 2 or more types.
- the amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst to be used, and further the reaction conditions, and is not particularly limited. It is preferable that it is a mass part.
- aldehydes are not necessarily required.
- a reaction solvent can be used.
- the reaction solvent in this polycondensation can be appropriately selected from known solvents and is not particularly limited. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. Illustrated.
- a solvent can be used individually by 1 type or in combination of 2 or more types.
- the amount of these solvents used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that it is the range of these.
- the reaction temperature can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C.
- the reaction method can be appropriately selected from known methods, and is not particularly limited.
- the reaction method may be a method in which the compound represented by the formula (0), the aldehyde and / or ketone, and a catalyst are charged together, There is a method in which a compound represented by the formula (0), an aldehyde and / or a ketone are dropped in the presence of a catalyst.
- the obtained compound can be isolated according to a conventional method, and is not particularly limited.
- a general method such as raising the temperature of the reaction vessel to 130 to 230 ° C. and removing volatile components at about 1 to 50 mmHg is adopted.
- a novolak resin as the target product can be obtained.
- the resin having the structure represented by the formula (3) may be a homopolymer of the compound represented by the formula (0), but is a copolymer with other phenols. May be.
- the copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Although propylphenol, pyrogallol, thymol, etc. are mentioned, it is not specifically limited to these.
- the resin having the structure represented by the formula (3) may be copolymerized with a polymerizable monomer other than the above-described phenols.
- the copolymerization monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene.
- the resin having the structure represented by the formula (3) is a binary or more (for example, a quaternary system) copolymer of the compound represented by the formula (1) and the above-described phenols. Even if it is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (1) and the above-mentioned copolymerization monomer, it is represented by the formula (1). It may be a ternary or more (for example, ternary to quaternary) copolymer of the above compound, the above-mentioned phenols, and the above-mentioned copolymerization monomer.
- the molecular weight of the resin having the structure represented by the formula (3) is not particularly limited, but the polystyrene equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20,000. Further, from the viewpoint of enhancing the crosslinking efficiency and suppressing the volatile components in the baking, the resin having the structure represented by the formula (3) has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. Those within the range of ⁇ 7 are preferred. The Mn can be obtained by the method described in Examples described later.
- the resin having the structure represented by the formula (3) is preferably highly soluble in a solvent from the viewpoint of easier application of a wet process. More specifically, when these compounds and / or resins use 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is 10% by mass or more. It is preferable that Here, the solubility in PGM and / or PGMEA is defined as “resin mass ⁇ (resin mass + solvent mass) ⁇ 100 (mass%)”. For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA is “10 mass% or more”, and when it is not dissolved, it is “less than 10 mass%”.
- R 0A has the same meaning as R Y
- R 1A is an n A valent group having 1 to 60 carbon atoms or a single bond
- R 2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
- the hydrogen atom is a group substituted with a hydroxyalkyl group or a glycidyl group
- the alkyl group, the aryl group, the alkenyl group, and the alkoxy group include an ether bond, a ketone bond, or an ester bond.
- R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
- n A has the same meaning as N above.
- n A is an integer of 2 or more
- the structural formulas in n A [] may be the same or different
- X A is synonymous with X
- m 2A is each independently an integer of 0 to 7, provided that at least one m 2A is an integer of 1 to 7;
- q A is each independently 0 or 1.
- R 0A has the same meaning as R Y described above.
- R 1A is an n A valent group having 1 to 60 carbon atoms or a single bond.
- n A is synonymous with N, and is an integer of 1 to 4.
- the structural formulas in n A [] may be the same or different.
- n-valent group examples include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group.
- the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.
- the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.
- R 2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
- the hydrogen atom is a group substituted with a hydroxyalkyl group or a glycidyl group
- the alkyl group, the aryl group, the alkenyl group, and the alkoxy group include an ether bond, a ketone bond, or an ester bond.
- At least one of R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- the alkyl group, alkenyl group and alkoxy group may be a linear, branched or cyclic group.
- X A is synonymous with X, and each independently represents an oxygen atom, a sulfur atom, or no bridge.
- X A is an oxygen atom or a sulfur atom, preferably because of the tendency to exhibit high heat resistance, and more preferably an oxygen atom.
- X A in terms of solubility, it is preferable that the non-crosslinked.
- m 2A is each independently an integer of 0 to 6. However, at least one m 2A is an integer of 1 to 6.
- q A is each independently 0 or 1.
- the compound represented by the formula (2) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. Moreover, it has tertiary carbon or quaternary carbon in the molecule, the crystallinity is suppressed, and it is suitably used as a film forming composition for lithography that can be used for manufacturing a film for lithography.
- the solubility in a safe solvent is high, the heat resistance and the etching resistance are good, and the resist forming composition for lithography according to this embodiment gives a good resist pattern shape.
- the film has a relatively low molecular weight and low viscosity, even a substrate having a step (particularly, a fine space or a hole pattern) can be uniformly filled to every corner of the step and the film can be flattened.
- the composition for forming an underlayer film for lithography using the same can be relatively advantageously enhanced in embedding and planarization characteristics.
- it is a compound having a relatively high carbon concentration, high etching resistance is also imparted.
- the aromatic density is high, the refractive index is high, and coloring is suppressed by a wide range of heat treatments from low to high temperatures, so that it is also useful as a composition for forming various optical parts.
- the one having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the present compound to suppress coloring, high heat resistance, and improving solvent solubility.
- Optical parts are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms It is useful as an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.
- the compound represented by the formula (2) is preferably a compound represented by the following formula (2-1) from the viewpoint of easy crosslinking and solubility in an organic solvent. (2-1)
- R 0A , R 1A , n A and q A and X A have the same meaning as described in the formula (2).
- R 3A is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, substituted
- An alkenyl group having 2 to 30 carbon atoms which may have a group, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group, and may be the same or different in the same naphthalene ring or benzene ring. May be.
- R 4A is each independently a hydrogen atom or a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group, wherein at least one of R 4A is a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group; m 6A is each independently an integer of 0 to 5.
- R 4A is a hydroxyalkyl group, glycidyl An oxyalkyl group or a glycidyl group;
- R 4A At least one of is a hydrogen atom.
- the compound represented by the formula (2-1) is preferably a compound represented by the following formula (2a).
- X A , R 0A to R 2A , m 2A and n A are as defined in the formula (2).
- the compound represented by the formula (2-1) is more preferably a compound represented by the following formula (2b).
- X A , R 0A , R 1A , R 3A , R 4A , m 6A and n A are as defined in the formula (2-1).
- the compound represented by the formula (2-1) is more preferably a compound represented by the following formula (2c).
- X A , R 0A , R 1A , R 3A , R 4A , m 6A and n A are as defined in the formula (2-1).
- the compound represented by the formula (2) is represented by the following formulas (BiN-1) to (BiN-4) or (XBiN-1) to (XBiN-3) from the viewpoint of further solubility in an organic solvent. It is particularly preferred that the compound be (R 4A in the specific examples is as defined above).
- the compound represented by the formula (2) used in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited.
- a polyphenol compound is obtained by polycondensation reaction of phenols, naphthols and the corresponding ketones under an acid catalyst under normal pressure, and subsequently, at least one phenolic hydroxyl group of the polyphenol compound is hydroxylated. It can be obtained by introducing an alkyl group or a glycidyl group, or further introducing a glycidyl group into the hydroxy group of the hydroxyalkyl group.
- combination can also be performed under pressure as needed.
- transduces a hydroxyalkyl group or a glycidyl group not only after the condensation reaction of naphthols and ketones but the stage before a condensation reaction may be sufficient. Moreover, you may carry out after manufacturing resin mentioned later.
- the timing for introducing the glycidyl group into the hydroxy group of the hydroxyalkyl group may be any stage after the introduction of the hydroxyalkyl group.
- the naphthols are not particularly limited, and examples thereof include naphthol, methyl naphthol, methoxy naphthol, naphthalene diol, and the like. It is more preferable to use naphthalene diol because a xanthene structure can be easily formed.
- the phenols are not particularly limited, and examples thereof include phenol, methylphenol, methoxybenzene, catechol, resorcinol, hydroquinone, and trimethylhydroquinone.
- ketones examples include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene.
- the acid catalyst is not particularly limited, and can be appropriately selected from known inorganic acids and organic acids.
- inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid; oxalic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalene
- Organic acids such as sulfonic acid and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid Can be mentioned.
- hydrochloric acid or sulfuric acid from the viewpoint of production such as availability and ease of handling.
- hydrochloric acid or sulfuric acid from the viewpoint of
- a reaction solvent may be used.
- the reaction solvent is not particularly limited as long as the reaction between the ketones to be used and naphthols proceeds.
- water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof can be used.
- the amount of the solvent is not particularly limited, and is, for example, in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material.
- the reaction temperature is not particularly limited and can be appropriately selected according to the reactivity of the reaction raw material, but is preferably in the range of 10 to 200 ° C.
- the lower the temperature, the higher the effect and the more preferable the range is 10 to 60 ° C.
- the manufacturing method of the said compound is not specifically limited, For example, there exist the method of charging naphthols etc., ketones, and a catalyst collectively, and the method of dripping naphthols and ketones in catalyst presence. After the polycondensation reaction, in order to remove unreacted raw materials, catalysts, etc. existing in the system, the temperature of the reaction vessel can be raised to 130 to 230 ° C., and volatile components can be removed at about 1 to 50 mmHg. .
- the amount of the raw material for producing the compound represented by the formula (2) is not particularly limited. For example, 2 moles to an excess amount of naphthols and the acid catalyst are added to 0.1 mole of 1 mole of aldehyde. The reaction proceeds by using 001-1 mol and reacting at 20-60 ° C. for 20 minutes to 100 hours at normal pressure.
- the target product is isolated by a known method after the completion of the reaction.
- the method for isolating the target product is not particularly limited.
- the reaction solution is concentrated, pure water is added to precipitate the reaction product, the solution is cooled to room temperature, filtered, and separated to obtain a solid product. After filtering and drying, a method of separating and purifying from by-products by column chromatography, evaporating the solvent, filtering and drying to obtain the target compound can be mentioned.
- a method for introducing a hydroxyalkyl group into at least one phenolic hydroxyl group of a polyphenol compound is also known.
- a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of the compound as follows.
- the hydroxyalkyl group may be introduced into the phenolic hydroxyl group via an oxyalkyl group.
- a hydroxyalkyloxyalkyl group or a hydroxyalkyloxyalkyloxyalkyl group is introduced.
- a compound for introducing a hydroxyalkyl group can be synthesized or easily obtained by a known method.
- chloroethanol bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide , Propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but are not particularly limited.
- a polyphenol compound and a compound for introducing the above hydroxyalkyl group are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
- an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
- metal alkoxide sodium methoxide, sodium ethoxide, potassium methoxide, alkali metal such as potassium ethoxide or alkaline earth metal alkoxide
- metal hydroxide sodium hydroxide, alkali metal such as potassium hydroxide
- alkaline earth metal carbonate etc.
- alkali metal such as sodium hydrogen carbonate, potassium hydrogen carbonate, or alkaline earth hydrogen carbonate
- amines for example, tertiary amines (trialkylamines such as triethylamine, N, N -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), carboxylic acid metal salts (alkali metal acetates or alkaline earth metal salts such as sodium acetate, calcium acetate, etc.) ) 20-15 at atmospheric pressure in the presence of a base catalyst such as an organic base The reaction is allowed to proceed
- the reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness.
- the compound in which the hydrogen atom of the hydroxyl group is substituted with a hydroxyalkylene group can be obtained by washing with distilled water if necessary and drying.
- a hydroxyethyl group is introduced by deacylation after an acetoxyethyl group is introduced.
- ethylene carbonate, propylene carbonate, or butylene carbonate a hydroxyalkyl group is introduced by adding an alkylene carbonate to cause a decarboxylation reaction.
- a glycidyl group can be introduced into at least one phenolic hydroxyl group or hydroxyalkyl group of the polyphenol compound as follows.
- a method of introducing a glycidyl group into the phenolic hydroxyl group or hydroxyalkyl group is also known.
- a compound for introducing a glycidyl group can be synthesized or easily obtained by a known method, and examples thereof include epichlorohydrin and epibromohydrin, but are not particularly limited.
- a polyphenol compound and the compound for introducing the glycidyl group described above are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
- an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
- metal alkoxide sodium methoxide, sodium ethoxide, potassium methoxide, alkali metal such as potassium ethoxide or alkaline earth metal alkoxide
- metal hydroxide sodium hydroxide, alkali metal such as potassium hydroxide
- alkaline earth metal carbonate etc.
- alkali metal such as sodium hydrogen carbonate, potassium hydrogen carbonate, or alkaline earth hydrogen carbonate
- amines for example, tertiary amines (trialkylamines such as triethylamine, N, N -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), carboxylic acid metal salts (alkali metal acetates or alkaline earth metal salts such as sodium acetate, calcium acetate, etc.) ) 20-15 at atmospheric pressure in the presence of a base catalyst such as an organic base The reaction is allowed to proceed
- reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness. Accordingly, the compound in which the hydrogen atom of the phenolic hydroxyl group or hydroxyalkyl group is substituted with a glycidyl group can be obtained by washing with distilled water and drying.
- the group substituted with a hydroxyalkyl group or a glycidyl group reacts in the presence of a radical or an acid / alkali, and has solubility in an acid, an alkali, or an organic solvent used in a coating solvent or a developer.
- the group substituted with a hydroxyalkyl group or a glycidyl group has a property of causing a chain reaction in the presence of a radical or an acid / alkali in order to enable pattern formation with higher sensitivity and higher resolution. preferable.
- the compound represented by the formula (2) can be used as it is as a film-forming composition for lithography. Moreover, it can be used also as resin obtained by using the compound represented by the said Formula (2) as a monomer. For example, it can also be used as a resin obtained by reacting a compound represented by the formula (2) with a compound having crosslinking reactivity.
- the resin obtained using the compound represented by the formula (2) as a monomer include those having a structure represented by the following formula (4). That is, the composition of the present embodiment may contain a resin having a structure represented by the following formula (4).
- L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent.
- the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond, R 0A , R 1A , R 2A , m 2A , n A , q A and X A are the same as those in the formula (2), When n A is an integer of 2 or more, the structural formulas in the n A [] may be the same or different. However, at least one of R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
- the resin of this embodiment can be obtained by reacting the compound represented by the formula (2) with a compound having a crosslinking reactivity.
- a known compound can be used without particular limitation as long as the compound represented by the formula (2) can be oligomerized or polymerized.
- Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.
- the resin having the structure represented by the formula (2) include, for example, a condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone having a crosslinking reaction. And a novolak resin.
- aldehyde for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde
- examples thereof include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural.
- ketones include the aforementioned ketones. Among these, formaldehyde is more preferable. In addition, these aldehydes and / or ketones can be used individually by 1 type or in combination of 2 or more types.
- the amount of the aldehyde and / or ketone used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 0.5 mol, relative to 1 mol of the compound represented by the formula (2). ⁇ 2 moles.
- a catalyst may be used.
- the acid catalyst used here can be appropriately selected from known ones and is not particularly limited.
- inorganic acids and organic acids are widely known.
- inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, and succinic acid.
- Adipic acid sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid Organic acids such as naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Although it is mentioned, it is not specifically limited to these.
- an organic acid or a solid acid is preferable from the viewpoint of manufacturing, and hydrochloric acid or sulfuric acid is preferable from the viewpoint of manufacturing such as availability and ease of handling.
- an acid catalyst 1 type can be used individually or in combination of 2 or more types.
- the amount of the acid catalyst used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0.01 to 100 per 100 parts by mass of the reactive raw material. It is preferable that it is a mass part.
- indene hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, ⁇ -pinene, ⁇ -pinene
- aldehydes are not necessarily required.
- a reaction solvent can be used in the condensation reaction between the compound represented by the formula (2) and the aldehyde and / or ketone.
- the reaction solvent in this polycondensation can be appropriately selected from known solvents and is not particularly limited. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. Illustrated.
- a solvent can be used individually by 1 type or in combination of 2 or more types.
- the amount of these solvents used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that it is the range of these.
- the reaction temperature can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C.
- the reaction method can be appropriately selected from known methods and is not particularly limited.
- the reaction method may be a method in which the compound represented by the formula (2), the aldehyde and / or ketone, and a catalyst are charged all together, There is a method in which a compound represented by the formula (2), an aldehyde and / or a ketone are added dropwise in the presence of a catalyst.
- the obtained compound can be isolated according to a conventional method, and is not particularly limited.
- a general method such as raising the temperature of the reaction vessel to 130 to 230 ° C. and removing volatile components at about 1 to 50 mmHg is adopted.
- a novolak resin as the target product can be obtained.
- the resin having the structure represented by the formula (4) may be a homopolymer of the compound represented by the formula (2), but is a copolymer with other phenols. May be.
- the copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Although propylphenol, pyrogallol, thymol, etc. are mentioned, it is not specifically limited to these.
- the resin having the structure represented by the formula (4) may be copolymerized with a polymerizable monomer other than the above-described phenols.
- the copolymerization monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene.
- the resin having the structure represented by the formula (2) is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (2) and the above-described phenols. Even in the case of a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (2) and the above-described copolymerization monomer, it is represented by the formula (2). It may be a ternary or more (for example, ternary to quaternary) copolymer of the above compound, the above-mentioned phenols, and the above-mentioned copolymerization monomer.
- the molecular weight of the resin having the structure represented by the formula (4) is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20,000. Further, from the viewpoint of increasing the crosslinking efficiency and suppressing the volatile components in the baking, the resin having the structure represented by the formula (4) has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. Those within the range of ⁇ 7 are preferred. The Mn can be obtained by the method described in Examples described later.
- the resin having the structure represented by the formula (4) is preferably highly soluble in a solvent from the viewpoint of easier application of a wet process. More specifically, when these compounds and / or resins use 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is 10% by mass or more. It is preferable that Here, the solubility in PGM and / or PGMEA is defined as “resin mass ⁇ (resin mass + solvent mass) ⁇ 100 (mass%)”. For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA is “10 mass% or more”, and when it is not dissolved, it is “less than 10 mass%”.
- the compound represented by the formula (0) and the resin obtained using this as a monomer can be purified by the following purification method. That is, the compound and / or resin purification method of the present embodiment includes a compound represented by the formula (0) and a resin obtained using the compound as a monomer (for example, a compound represented by the formula (1), the formula A resin obtained using the compound represented by (1) as a monomer, one or more selected from a compound represented by the formula (2) and a resin obtained using the compound represented by the formula (2) as a monomer) A step of obtaining a solution (S) by dissolving in a solvent, and a step of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the compound and / or the resin (first extraction) And a solvent used in the step of obtaining the solution (S) includes an organic solvent that is arbitrarily immiscible with water.
- a solvent used in the step of obtaining the solution (S) includes an organic solvent that is arbitrarily immis
- the resin is, for example, a resin obtained by a reaction between the compound represented by the formula (1) and / or the compound represented by the formula (2) and a compound having a crosslinking reaction.
- a resin obtained by a reaction between the compound represented by the formula (1) and / or the compound represented by the formula (2) and a compound having a crosslinking reaction Preferably there is.
- the purification method content of the various metals which can be contained as an impurity in the compound or resin which has the specific structure mentioned above can be reduced. More specifically, in the purification method, the compound and / or the resin is dissolved in an organic solvent that is arbitrarily immiscible with water to obtain a solution (S), and the solution (S) is further converted into an acidic aqueous solution.
- the extraction process can be performed by contact. Thereby, after transferring the metal content contained in the solution (S) to the aqueous phase, the organic phase and the aqueous phase can be separated to obtain a compound and / or resin having a reduced
- the compound and resin used in the purification method may be used alone or in combination of two or more.
- the said compound and resin may contain various surfactant, various crosslinking agents, various acid generators, various stabilizers, etc.
- the solvent that is arbitrarily miscible with water used in the purification method is not particularly limited, but is preferably an organic solvent that can be safely applied to a semiconductor manufacturing process. Specifically, the solubility in water at room temperature is 30%.
- the organic solvent is less than 20%, more preferably less than 20%, particularly preferably less than 10%.
- the amount of the organic solvent used is preferably 1 to 100 times by mass with respect to the total amount of the compound to be used and the resin.
- ethers such as diethyl ether and diisopropyl ether
- esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate, methyl ethyl ketone, and methyl isobutyl.
- Ketones such as ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone; ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl Glycol ether acetates such as ether acetate; Aliphatic hydrocarbons such as n-hexane and n-heptane; Aromatic hydrocarbons such as toluene and xylene Methylene chloride, halogenated hydrocarbons such as chloroform and the like.
- toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferable, More preferred are methyl isobutyl ketone and ethyl acetate. Methyl isobutyl ketone, ethyl acetate, etc.
- solvents are removed when the solvent is industrially distilled off or dried because the compound and the resin containing the compound as a constituent component have a relatively high saturation solubility and a relatively low boiling point. It is possible to reduce the load in the process.
- These solvents can be used alone or in combination of two or more.
- the acidic aqueous solution used in the purification method is appropriately selected from aqueous solutions in which generally known organic compounds or inorganic compounds are dissolved in water.
- a mineral acid aqueous solution in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like is dissolved in water, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid
- acidic aqueous solutions can be used alone or in combination of two or more.
- one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid,
- One or more organic acid aqueous solutions selected from the group consisting of tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid are preferred, and sulfuric acid, nitric acid, acetic acid, oxalic acid,
- An aqueous solution of carboxylic acid such as tartaric acid and citric acid is more preferable
- an aqueous solution of sulfuric acid, succinic acid, tartaric acid and citric acid is more preferable, and
- the pH of the acidic aqueous solution used in the purification method is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the compound and the resin.
- the pH range is about 0 to 5, preferably about pH 0 to 3.
- the amount of the acidic aqueous solution used in the purification method is not particularly limited, but from the viewpoint of reducing the number of extractions for metal removal and from the viewpoint of securing operability in consideration of the total amount of liquid, the amount used is It is preferable to adjust. From the above viewpoint, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, and more preferably 20 to 100% by mass with respect to 100% by mass of the solution (S).
- a metal component can be extracted from the compound or the resin in the solution (S) by bringing the acidic aqueous solution into contact with the solution (S).
- the solution (S) further contains an organic solvent arbitrarily mixed with water.
- an organic solvent arbitrarily mixed with water is included, the amount of the compound and / or resin charged can be increased, the liquid separation property is improved, and purification can be performed with high pot efficiency.
- the method for adding an organic solvent arbitrarily mixed with water is not particularly limited.
- any of a method of adding to a solution containing an organic solvent in advance, a method of adding to water or an acidic aqueous solution in advance, and a method of adding after bringing a solution containing an organic solvent into contact with water or an acidic aqueous solution may be used.
- the method of adding to the solution containing an organic solvent in advance is preferable from the viewpoint of the workability of the operation and the ease of management of the charged amount.
- the organic solvent arbitrarily mixed with water used in the purification method is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable.
- the amount of the organic solvent arbitrarily mixed with water is not particularly limited as long as the solution phase and the aqueous phase are separated from each other, but is 0.1 to 100 times by mass with respect to the total amount of the compound and the resin to be used. It is preferably 0.1 to 50 times by mass, more preferably 0.1 to 20 times by mass.
- organic solvent arbitrarily mixed with water used in the purification method include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol and isopropanol; acetone And ketones such as N-methylpyrrolidone; aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether.
- ethers such as tetrahydrofuran and 1,3-dioxolane
- alcohols such as methanol, ethanol and isopropanol
- acetone And ketones such as N-methylpyrrolidone
- aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glyco
- N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable.
- These solvents can be used alone or in combination of two or more.
- the temperature at the time of the extraction treatment is usually 20 to 90 ° C, preferably 30 to 80 ° C.
- the extraction operation is performed, for example, by mixing the mixture well by stirring or the like and then allowing it to stand. Thereby, the metal part contained in solution (S) transfers to an aqueous phase. Moreover, the acidity of a solution falls by this operation and the quality change of a compound and / or resin can be suppressed.
- the solution phase is recovered by decantation or the like.
- the standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation between the solvent-containing solution phase and the aqueous phase.
- the time for standing is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
- the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times.
- the solution phase containing the compound or the resin is further brought into contact with water to extract impurities in the compound or the resin (second extraction step). It is preferable. Specifically, for example, after performing the extraction treatment using an acidic aqueous solution, the solution phase containing the compound and / or resin and solvent extracted and recovered from the aqueous solution is further subjected to an extraction treatment with water. It is preferable.
- the above-described extraction treatment with water is not particularly limited. For example, after the solution phase and water are mixed well by stirring or the like, the obtained mixed solution can be left still.
- the solution phase can be recovered by decantation or the like.
- the water used here is water with a small metal content, for example, ion-exchanged water or the like in accordance with the purpose of the present embodiment.
- the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times. Further, the use ratio of both in the extraction process, conditions such as temperature and time are not particularly limited, but they may be the same as those in the contact process with the acidic aqueous solution.
- the water that can be mixed into the solution containing the compound and / or resin and solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. Moreover, a solvent can be added to the said solution as needed, and the density
- the method for isolating the compound and / or resin from the solution containing the obtained compound and / or resin and solvent is not particularly limited, and known methods such as removal under reduced pressure, separation by reprecipitation, and combinations thereof. Can be done. If necessary, known processes such as a concentration operation, a filtration operation, a centrifugal separation operation, and a drying operation can be performed.
- composition contains 1 or more types chosen from the group which consists of a compound and resin of the above-mentioned this embodiment.
- the composition of this embodiment can further contain a solvent, an acid generator, a crosslinking agent, a crosslinking accelerator, a radical polymerization initiator, and the like.
- the composition of the present embodiment can be used for a film forming application for lithography (that is, a film forming composition for lithography) and an optical component forming application.
- the composition of the present embodiment is one or more selected from the group consisting of the compound of the present embodiment and a resin (for example, a compound represented by the formula (1), a compound represented by the formula (1) Resin as a monomer, one or more selected from the group consisting of a compound represented by the formula (2) and a resin obtained by using the compound represented by the formula (2) as a monomer) as a resist base material can do.
- a resin for example, a compound represented by the formula (1), a compound represented by the formula (1) Resin as a monomer, one or more selected from the group consisting of a compound represented by the formula (2) and a resin obtained by using the compound represented by the formula (2) as a monomer
- the composition of this embodiment can be used as a film-forming composition for lithography for chemical amplification resist applications (hereinafter also referred to as a resist composition).
- the resist composition contains, for example, one or more selected from the group consisting of the compound and resin of the present embodiment.
- the resist composition preferably contains a solvent.
- the solvent include, but are not limited to, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate.
- Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono -Propylene glycol such as n-butyl ether acetate Cole monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, etc.
- PGMEA propylene glycol monomethyl ether acetate
- PGMEA propylene glycol monoethyl ether acetate
- Lactate esters aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyrate Other esters such as acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptan
- the solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate.
- a seed more preferably at least one selected from PGMEA, PGME and CHN.
- the amount of the solid component and the amount of the solvent are not particularly limited, but 1 to 80% by weight of the solid component and 20 to 99% of the solvent with respect to 100% by weight of the total amount of the solid component and the solvent.
- the solid component is preferably 1 to 50% by mass, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, further preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably solid
- the component is 2 to 10% by mass and the solvent is 90 to 98% by mass.
- the resist composition contains, as another solid component, at least one selected from the group consisting of an acid generator (C), a crosslinking agent (G), an acid diffusion controller (E), and other components (F). May be.
- a solid component means components other than a solvent.
- the acid generator (C), the crosslinking agent (G), the acid diffusion controller (E) and other components (F), known ones can be used, and are not particularly limited. Those described in Japanese Patent No. / 024778 are preferable.
- the content of the compound and resin of the above-described embodiment used as a resist base material is not particularly limited, but the total mass of the solid components (resist base material, acid generator (C), cross-linking agent ( G), the total amount of solid components including optionally used components such as the acid diffusion controller (E) and other components (F), the same shall apply hereinafter)) is preferably 50 to 99.4% by mass, More preferred is 55 to 90% by mass, still more preferred is 60 to 80% by mass, and particularly preferred is 60 to 70% by mass. In the case of the content, the resolution is further improved and the line edge roughness (LER) is further reduced. In addition, when containing both a compound and resin as a resist base material, the said content is the total amount of both components.
- additives such as thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc. 1 type (s) or 2 or more types can be added.
- another component (F) may be called arbitrary component (F).
- contents of a resist base material (hereinafter also referred to as component (A)), an acid generator (C), a crosslinking agent (G), an acid diffusion controller (E), and an optional component (F)
- component (A) / Acid generator (C) / Crosslinking agent (G) / Acid diffusion controller (E) / Optional component (F)
- component (A) is mass% based on solid matter, Preferably 50 to 99.4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49/0 to 49, More preferably 55 to 90/1 to 40 / 0.5 to 40 / 0.01 to 10/0 to 5, More preferably 60 to 80/3 to 30/1 to 30 / 0.01 to 5/0 to 1, Particularly preferred is 60 to 70/10 to 25/2 to 20 / 0.01 to 3/0.
- the blending ratio of each component is selected from each range so that the sum is 100% by mass. When the above composition is used, the performance such as sensitivity, resolution and developability is excellent.
- the resist composition is usually prepared by dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering with a filter having a pore size of about 0.2 ⁇ m, for example, as necessary.
- the resist composition may contain a resin other than the compound and resin of the present embodiment as long as the object of the present invention is not impaired.
- the resin is not particularly limited, and for example, a novolac resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and a polymer containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units. A combination or a derivative thereof may be used.
- the content of the resin is not particularly limited and is appropriately adjusted according to the type of the component (A) to be used, but is preferably 30 parts by mass or less, more preferably 100 parts by mass of the component (A). It is 10 mass parts or less, More preferably, it is 5 mass parts or less, Most preferably, it is 0 mass part.
- the resist composition can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process. Either a positive resist pattern or a negative resist pattern can be created depending on the type of compound and resin of the present embodiment and / or the type of developer used.
- the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developing solution at 23 ° C. is preferably 5 ⁇ / sec or less, more preferably 0.05 to 5 ⁇ / sec, More preferred is .0005 to 5 liters / sec.
- the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist.
- the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed that the contrast between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer increases due to the change in solubility of the compound and resin of the present embodiment before and after exposure. Is done.
- the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developer at 23 ° C. is preferably 10 ⁇ / sec or more.
- the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developer and more suitable for a resist.
- the dissolution rate is 10 ⁇ / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the compound and resin of the present embodiment described above dissolves and LER is reduced. There is also an effect of reducing defects.
- the dissolution rate can be determined by immersing the amorphous film in a developer at a temperature of 23 ° C. for a predetermined time, and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method.
- the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developer at 23 ° C. at a portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray is It is preferably 10 ⁇ / sec or more.
- the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developer and more suitable for a resist.
- the dissolution rate is 10 ⁇ / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the compound and resin of the present embodiment described above dissolves and LER is reduced. There is also an effect of reducing defects.
- the dissolution rate in a developing solution at 23 ° C. of a portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray of an amorphous film formed by spin coating the resist composition is 5 ⁇ / sec or less is preferable, 0.05 to 5 ⁇ / sec is more preferable, and 0.0005 to 5 ⁇ / sec is more preferable.
- the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist.
- the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved.
- the composition of this embodiment can be used as a film-forming composition for lithography for non-chemically amplified resist applications (hereinafter also referred to as a radiation-sensitive composition).
- the component (A) (the compound and resin of the above-described embodiment) contained in the radiation-sensitive composition is used in combination with the diazonaphthoquinone photoactive compound (B) described later, and g-line, h-line, i-line, KrF.
- a positive resist substrate that becomes a compound that is easily soluble in a developer by irradiation with an excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray.
- G-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray does not change the property of component (A) greatly, but diazonaphthoquinone photoactivity is hardly soluble in the developer.
- the component (A) contained in the radiation-sensitive composition is a compound having a relatively low molecular weight, the roughness of the obtained resist pattern is very small.
- at least one selected from the group consisting of R 0 to R 5 is preferably a group containing an iodine atom.
- R 0A , R 1A and R 2A It is preferable that at least one selected from the group consisting of is a group containing an iodine atom.
- the glass transition temperature of the component (A) (resist base material) contained in the radiation-sensitive composition is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. It is. Although the upper limit of the glass transition temperature of a component (A) is not specifically limited, For example, it is 400 degreeC. When the glass transition temperature of the component (A) is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape, and performance such as high resolution is improved.
- the crystallization calorific value obtained by differential scanning calorimetric analysis of the glass transition temperature of the component (A) contained in the radiation-sensitive composition is preferably less than 20 J / g.
- (crystallization temperature) ⁇ glass transition temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher.
- crystallization heat generation amount is less than 20 J / g, or (crystallization temperature) ⁇ (glass transition temperature) is in the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.
- the crystallization heat generation amount, the crystallization temperature, and the glass transition temperature can be obtained by differential scanning calorimetry using DSC / TA-50WS manufactured by Shimadzu Corporation.
- About 10 mg of a sample is put into an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 mL / min).
- the temperature is raised again to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 mL / min). Further, after rapid cooling, the temperature is increased again to 400 ° C.
- the temperature at the midpoint of the step difference of the baseline that has changed in a step shape is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature.
- Tg glass transition temperature
- the calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.
- the component (A) contained in the radiation-sensitive composition is sublimated under normal pressure at 100 or less, preferably 120 ° C. or less, more preferably 130 ° C. or less, further preferably 140 ° C. or less, particularly preferably 150 ° C. or less. It is preferable that the property is low.
- the low sublimation property means that in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, particularly preferably. Indicates 0.1% or less. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. In addition, a good pattern shape can be obtained with low roughness.
- Component (A) contained in the radiation-sensitive composition is propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, A solvent selected from butyl acetate, ethyl propionate and ethyl lactate and having the highest solubility in component (A) at 23 ° C., preferably 1% by mass or more, more preferably 5% by mass or more, More preferably 10% by mass or more, particularly preferably selected from PGMEA, PGME, CHN, and (A) 20% by mass or more at 23 ° C. in a solvent having the highest solubility in the resist base material, Particularly preferably, it dissolves in PGMEA at 20 ° C. or more at 23 ° C.
- the semiconductor manufacturing process can be used in actual production.
- the diazonaphthoquinone photoactive compound (B) contained in the radiation-sensitive composition is a diazonaphthoquinone substance containing a polymeric and non-polymeric diazonaphthoquinone photoactive compound.
- a photosensitive component As long as it is used as (photosensitive agent), one or two or more kinds can be arbitrarily selected and used without particular limitation.
- a photosensitizer it was obtained by reacting naphthoquinone diazide sulfonic acid chloride, benzoquinone diazide sulfonic acid chloride, etc. with a low molecular compound or a high molecular compound having a functional group capable of condensation reaction with these acid chlorides.
- Compounds are preferred.
- the functional group capable of condensing with acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, and a hydroxyl group is particularly preferable.
- the compound capable of condensing with an acid chloride containing a hydroxyl group is not particularly limited.
- hydroquinone, resorcin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2 ′, 3,4,6′- Hydroxybenzophenones such as pentahydroxybenzophenone, hydroxyphenylalkanes such as bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane 4,4 ', 3 ", 4" -tetrahydroxy-3,5, Hydroxytriphenylmethane such as 3 ', 5'-tetramethyltriphenylmethane, 4,4', 2 ", 3", 4 "-pentahydroxy-3,5,3 ', 5'-tetrate
- acid chlorides such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride, and the like. Can be mentioned.
- the radiation-sensitive composition is prepared by, for example, dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering, for example, with a filter having a pore size of about 0.2 ⁇ m as necessary. Is preferred.
- the radiation-sensitive composition can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process. Depending on the type of developer used, either a positive resist pattern or a negative resist pattern can be created.
- the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition in a developing solution at 23 ° C. is preferably 5 ⁇ / sec or less, more preferably 0.05 to 5 ⁇ / sec. 0.0005 to 5 cm / sec is more preferable. When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist.
- the dissolution rate when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is due to the contrast of the interface between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer due to a change in the solubility of the resin containing the compound and resin of the present embodiment as constituents before and after exposure. Is estimated to be larger. Further, there is an effect of reducing LER and reducing defects.
- the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition in a developing solution at 23 ° C. is preferably 10 ⁇ / sec or more.
- the dissolution rate When the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developer and more suitable for a resist. Further, when the dissolution rate is 10 ⁇ / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the resin containing the compound and resin of the present embodiment described above as constituent components dissolves and LER is reduced. There is also an effect of reducing defects.
- the dissolution rate can be determined by immersing the amorphous film in a developer at a temperature of 23 ° C. for a predetermined time, and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method.
- the amorphous film formed by spin-coating the radiation-sensitive composition is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or at 20 to 500 ° C.
- the dissolution rate of the exposed portion after heating in the developing solution at 23 ° C. is preferably 10 ⁇ / sec or more, more preferably 10 to 10000 ⁇ / sec, and further preferably 100 to 1000 ⁇ / sec.
- the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developer and more suitable for a resist.
- the dissolution rate is 10000 kg / sec or less, the resolution may be improved.
- the amorphous film formed by spin-coating the radiation-sensitive composition is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or at 20 to 500 ° C.
- the dissolution rate of the exposed portion after heating with respect to the developer at 23 ° C. is preferably 5 K / sec or less, more preferably 0.05 to 5 K / sec, and further preferably 0.0005 to 5 K / sec.
- the resist When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed that the contrast of the unexposed portion that dissolves in the developer and the interface between the exposed portion that does not dissolve in the developer increases due to the change in solubility of the compound and resin of the present embodiment before and after exposure. Is done. Further, there is an effect of reducing LER and reducing defects.
- the content of the component (A) is the solid component total weight (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc.)
- the total of the components is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass.
- the radiation-sensitive composition can obtain a pattern with high sensitivity and small roughness.
- the content of the diazonaphthoquinone photoactive compound (B) is arbitrarily selected from the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B), and other components (D)).
- the total of solid components used, the same shall apply hereinafter) is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25 to 75%. % By mass.
- the radiation-sensitive composition of the present embodiment can obtain a highly sensitive and small roughness pattern.
- an acid generator In the radiation-sensitive composition, an acid generator, a cross-linking agent, an acid may be used as a component other than the component (A) and the diazonaphthoquinone photoactive compound (B) as necessary, as long as the object of the present invention is not impaired.
- Diffusion control agent dissolution accelerator, dissolution control agent, sensitizer, surfactant, organic carboxylic acid or phosphorus oxo acid or derivative thereof, heat and / or photocuring catalyst, polymerization inhibitor, flame retardant, filler, Coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc.
- Another component (D) may be called arbitrary component (D).
- the blending ratio of each component is mass% based on the solid component, Preferably 1 to 99/99 to 1/0 to 98, More preferably 5 to 95/95 to 5/0 to 49, More preferably, 10 to 90/90 to 10/0 to 10, Particularly preferably 20 to 80/80 to 20/0 to 5, Most preferably, it is 25 to 75/75 to 25/0.
- the blending ratio of each component is selected from each range so that the sum is 100% by mass.
- the radiation-sensitive composition is excellent in performance such as sensitivity and resolution in addition to roughness when the blending ratio of each component is in the above range.
- the radiation-sensitive composition may contain compounds and resins other than the present embodiment as long as the object of the present invention is not impaired.
- resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units, or these resins. Derivatives and the like.
- the compounding quantity of these resin is suitably adjusted according to the kind of component (A) to be used, 30 mass parts or less are preferable with respect to 100 mass parts of components (A), More preferably, 10 mass parts or less More preferably, it is 5 parts by mass or less, and particularly preferably 0 part by mass.
- the method for forming a resist pattern according to the present embodiment includes forming a photoresist layer using the above-described composition of the present embodiment (the resist composition or the radiation sensitive composition), and then a predetermined region of the photoresist layer. And a step of performing development by irradiating the substrate with radiation.
- the method for forming a resist pattern according to the present embodiment includes a step of forming a resist film on a substrate, a step of exposing the formed resist film, and developing the resist film to form a resist pattern.
- the resist pattern in this embodiment can also be formed as an upper layer resist in a multilayer process.
- the method for forming the resist pattern is not particularly limited, and examples thereof include the following methods.
- a resist film is formed by applying the resist composition or radiation sensitive composition on a conventionally known substrate by a coating means such as spin coating, cast coating, roll coating or the like.
- the conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. Further, if necessary, an inorganic and / or organic film may be provided on the substrate.
- inorganic BARC inorganic antireflection film
- organic BARC organic antireflection film
- Surface treatment with hexamethylene disilazane or the like may be performed.
- the coated substrate is heated as necessary.
- the heating conditions vary depending on the composition of the resist composition, but are preferably 20 to 250 ° C., more preferably 20 to 150 ° C. Heating may improve the adhesion of the resist to the substrate, which is preferable.
- the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam.
- the exposure conditions and the like are appropriately selected according to the composition of the resist composition or the radiation sensitive composition.
- heating is preferably performed after radiation irradiation.
- the heating conditions vary depending on the composition of the resist composition or the radiation-sensitive composition, but are preferably 20 to 250 ° C, more preferably 20 to 150 ° C.
- a predetermined resist pattern is formed by developing the exposed resist film with a developer.
- a solvent having a solubility parameter (SP value) close to that of the compound and resin of the above-described embodiment to be used ketone solvent, ester solvent, alcohol solvent, amide solvent.
- SP value solubility parameter
- a polar solvent such as a solvent, an ether solvent, a hydrocarbon solvent, or an alkaline aqueous solution can be used.
- ketone solvent examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone.
- ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3 -Ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate and the like.
- the alcohol solvent examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, Alcohols such as 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene Glycol monoethyl ether, and triethylene glycol monoethyl ether and methoxymethyl butanol.
- Alcohols such as 4-methyl-2-pentanol, n-heptyl alcohol, n
- ether solvent examples include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
- amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
- hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
- the water content of the developer as a whole is less than 70% by mass, preferably less than 50% by mass, and more preferably less than 30% by mass.
- it is more preferably less than 10% by mass, and it is particularly preferable that it contains substantially no water.
- the content of the organic solvent with respect to the developer is 30% by mass to 100% by mass, preferably 50% by mass to 100% by mass, and preferably 70% by mass to 100% by mass with respect to the total amount of the developer. More preferably, it is 90 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less, It is especially preferable that it is 95 mass% or more and 100 mass% or less.
- alkaline aqueous solution examples include alkaline compounds such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline. Can be mentioned.
- alkaline compounds such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline. Can be mentioned.
- the developer is a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, such as resist pattern resolution and roughness. It is preferable for improving the resist performance.
- the vapor pressure of the developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
- vapor pressure of 5 kPa or less examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl Ketone solvents such as isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate
- Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone.
- Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ester solvents such as ethyl lactate, butyl lactate and propyl lactate, n-butyl alcohol alcohol solvents such as sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol , Glycol solvents such as triethylene glycol, and
- the surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
- fluorine and / or silicon surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950.
- Nonionic surfactant it is a nonionic surfactant.
- a fluorochemical surfactant or a silicon-type surfactant is more preferable to use.
- the amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.
- a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer application nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) ) Etc.
- the time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.
- a step of stopping development may be performed while substituting with another solvent.
- the rinsing liquid used in the rinsing step after development is not particularly limited as long as the resist pattern cured by crosslinking is not dissolved, and a solution or water containing a general organic solvent can be used.
- a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents.
- a cleaning step is performed using a rinse solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents.
- a washing step is performed using a rinse solution containing an alcohol solvent or an ester solvent. Even more preferably, after the development, a step of washing with a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after the development, a washing step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms.
- the time for rinsing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.
- examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, 3-methyl- 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2- Heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used.
- Particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4 -Methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It is possible to have.
- a plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.
- the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.
- the vapor pressure of the rinsing solution used after development is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less.
- An appropriate amount of a surfactant can be added to the rinse solution.
- the developed wafer is cleaned using a rinsing solution containing the organic solvent described above.
- the method of the cleaning treatment is not particularly limited.
- a method of continuously applying the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time.
- a method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied.
- a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
- the pattern wiring board is obtained by etching.
- the etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.
- Plating can be performed after forming the resist pattern.
- Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.
- the residual resist pattern after etching can be peeled off with an organic solvent.
- organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), and the like.
- peeling method include a dipping method and a spray method.
- the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.
- the wiring substrate obtained in this embodiment can also be formed by a method of depositing a metal in a vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.
- the composition of this embodiment can also be used as a film forming composition for lithography for use in lower layer films (hereinafter also referred to as a lower layer film forming material).
- the lower layer film-forming material contains at least one substance selected from the group consisting of the compound and resin of the above-described embodiment.
- the substance is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and more preferably 50 to 100% by mass in the lower layer film-forming material from the viewpoints of coatability and quality stability. % Is more preferable, and 100% by mass is particularly preferable.
- the lower layer film forming material can be applied to a wet process and has excellent heat resistance and etching resistance. Furthermore, since the material for forming the lower layer film uses the substance, it is possible to form a lower layer film that suppresses deterioration of the film during high-temperature baking and has excellent etching resistance against oxygen plasma etching and the like. Furthermore, since the lower layer film forming material is also excellent in adhesion to the resist layer, an excellent resist pattern can be obtained.
- the underlayer film forming material may contain a known underlayer film forming material for lithography and the like as long as the effects of the present invention are not impaired.
- the lower layer film forming material may contain a solvent.
- a solvent used for the lower layer film forming material a known one can be appropriately used as long as it can dissolve at least the above-described substances.
- the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cellosolv solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate and methyl acetate Ester solvents such as ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol, 1-ethoxy-2-propanol; toluene, xylene And aromatic hydrocarbons such as anisole. These solvents can be used alone or in combination of two or more.
- ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and
- cyclohexanone propylene glycol monomethyl ether
- propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate
- ethyl lactate methyl hydroxyisobutyrate
- anisole is particularly preferable from the viewpoint of safety.
- the content of the solvent is not particularly limited, but from the viewpoint of solubility and film formation, it is preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of the lower layer film-forming material, and 200 to 5, The amount is more preferably 000 parts by mass, and even more preferably 200 to 1,000 parts by mass.
- the lower layer film-forming material may contain a crosslinking agent as necessary from the viewpoint of suppressing intermixing.
- a crosslinking agent which can be used in this embodiment is not specifically limited, For example, the crosslinking agent as described in international publication 2013/024779 can be used.
- crosslinking agent examples include, for example, phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanates. Examples thereof include, but are not limited to, compounds and azide compounds.
- crosslinking agents can be used alone or in combination of two or more. Among these, a benzoxazine compound, an epoxy compound, or a cyanate compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improving etching resistance.
- phenol compound known compounds can be used.
- phenols include phenols, alkylphenols such as cresols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalenediols, and bisphenols such as bisphenol A and bisphenol F.
- polyfunctional phenol compounds such as phenol novolac and phenol aralkyl resin.
- aralkyl type phenol resins are preferable from the viewpoint of heat resistance and solubility.
- epoxy compound known compounds can be used and selected from those having two or more epoxy groups in one molecule.
- These epoxy resins may be used alone or in combination of two or more. From the viewpoint of heat resistance and solubility, an epoxy resin that is solid at room temperature such as an epoxy resin obtained from phenol aralkyl resins or biphenyl aralkyl resins is preferable.
- the cyanate compound is not particularly limited as long as it is a compound having two or more cyanate groups in one molecule, and a known one can be used.
- a preferred cyanate compound one having a structure in which a hydroxyl group of a compound having two or more hydroxyl groups in one molecule is substituted with a cyanate group can be mentioned.
- the cyanate compound preferably has an aromatic group, and a cyanate compound having a structure in which the cyanate group is directly connected to the aromatic group can be suitably used.
- cyanate compounds include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethylbisphenol F, bisphenol A novolac resin, bromine.
- Bisphenol A brominated phenol novolak resin, trifunctional phenol, tetrafunctional phenol, naphthalene type phenol, biphenyl type phenol, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, alicyclic phenol, phosphorus
- cyanate compounds may be used alone or in combination of two or more. Further, the cyanate compound described above may be in any form of a monomer, an oligomer and a resin.
- amino compound examples include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl Sulfide, 3,3′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene
- benzoxazine compound examples include Pd-type benzoxazine obtained from bifunctional diamines and monofunctional phenols, and Fa-type benzoxazine obtained from monofunctional diamines and bifunctional phenols. It is done.
- the melamine compound examples include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl.
- examples thereof include compounds in which 1 to 6 methylol groups of melamine and hexamethylolmelamine are acyloxymethylated, or a mixture thereof.
- the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine And compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof.
- glycoluril compound examples include, for example, tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, Examples thereof include compounds in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated, or mixtures thereof.
- urea compound examples include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated or a mixture thereof, tetramethoxyethyl urea, and the like.
- a crosslinking agent having at least one allyl group may be used from the viewpoint of improving the crosslinkability.
- Specific examples of the crosslinking agent having at least one allyl group include 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2 -Bis (3-allyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) ) Allylphenols such as ether, 2,2-bis (3-allyl-4-cyanatophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3 -Allyl-4-cyanatophenyl) propane, bis (3-allyl-4-cyanatosiphenyl) sulfone, bis (3-allyl-4-cyanatophenyl) sulfide, bis (3- Examples
- 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-hydroxyphenyl) Preference is given to allylphenols such as propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) ether.
- the content of the crosslinking agent in the composition is not particularly limited, but is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the total composition including the above-described compound or resin.
- the amount is more preferably part by mass, and further preferably 10 to 40 parts by mass.
- Crosslinking accelerator In the lower layer film forming material of the present embodiment, a crosslinking accelerator for accelerating the crosslinking and curing reaction can be used as necessary.
- the crosslinking accelerator is not particularly limited as long as it promotes crosslinking and curing reaction, and examples thereof include amines, imidazoles, organic phosphines, and Lewis acids. These crosslinking accelerators can be used alone or in combination of two or more. Among these, imidazoles or organic phosphines are preferable, and imidazoles are more preferable from the viewpoint of lowering the crosslinking temperature.
- crosslinking accelerator examples include, but are not limited to, for example, 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino).
- Tertiary amines such as methyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5- Imidazoles such as triphenylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium tetraphenylborate, teto Tetraphenyl such as phenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, etc., 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine /
- the content of the crosslinking accelerator is usually preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass when the total mass of the composition is 100 parts by mass. From the viewpoint of ease and economy, it is 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass.
- a radical polymerization initiator can be blended as necessary.
- the radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization with light or a thermal polymerization initiator that initiates radical polymerization with heat.
- the radical polymerization initiator can be, for example, at least one selected from the group consisting of ketone photopolymerization initiators, organic peroxide polymerization initiators, and azo polymerization initiators.
- Such a radical polymerization initiator is not particularly limited, and those conventionally used can be appropriately employed.
- 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] Dihydride chloride, 2,2′-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2, '-Azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2
- the content of the radical polymerization initiator may be any stoichiometrically required amount, but 0.05 to 25 masses when the total mass of the composition containing the compound or resin is 100 mass parts. Part is preferable, and 0.1 to 10 parts by mass is more preferable.
- the content of the radical polymerization initiator is 0.05 parts by mass or more, there is a tendency that curing can be prevented from being insufficient.
- the content of the radical polymerization initiator is 25 parts by mass or less. In such a case, the long-term storage stability of the lower layer film-forming material at room temperature tends to be prevented from being impaired.
- the lower layer film-forming material may contain an acid generator as required from the viewpoint of further promoting the crosslinking reaction by heat.
- an acid generator those that generate an acid by thermal decomposition and those that generate an acid by light irradiation are known, and any of them can be used. For example, those described in International Publication No. 2013/024779 can be used.
- the content of the acid generator is not particularly limited, but is preferably 0.1 to 50 parts by weight, more preferably 0.5 parts by weight with respect to 100 parts by weight of the lower layer film forming material. ⁇ 40 parts by mass.
- the lower layer film-forming material may contain a basic compound from the viewpoint of improving storage stability.
- the basic compound serves as a quencher for the acid to prevent the acid generated in a trace amount from the acid generator from causing the crosslinking reaction to proceed.
- a basic compound is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.
- the content of the basic compound is not particularly limited, but is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 100 parts by mass of the lower layer film forming material. ⁇ 1 part by mass.
- the lower layer film forming material in the present embodiment may contain other resins and / or compounds for the purpose of imparting curability by heat or light and controlling the absorbance.
- other resins and / or compounds include naphthol resins, xylene resins, naphthol-modified resins, phenol-modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth) acrylates, dimethacrylates, trimethacrylates, tetra Resins containing no heterocyclic ring or aromatic ring such as methacrylate, vinyl naphthalene, polyacenaphthylene and other naphthalene rings, phenanthrenequinone, biphenyl rings such as fluorene, hetero rings having hetero atoms such as thiophene and indene; rosin resins; Examples thereof include resins or compounds containing an alicyclic structure such
- the lower layer film-forming material in the present embodiment may contain a known additive.
- the known additives include, but are not limited to, for example, heat and / or photocuring catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photocurable resins, dyes, Examples thereof include pigments, thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, and nonionic surfactants.
- the lower layer film for lithography can be formed using the lower layer film forming material.
- a step (A-1) of forming a lower layer film on the substrate using the lower layer film forming material (the composition of the present embodiment), and at least one photoresist layer is formed on the lower layer film.
- a resist pattern forming method comprising: a forming step (A-2); and a step (A-3) of irradiating a predetermined region of the photoresist layer with radiation after the second forming step and developing Can be used.
- another pattern forming method (circuit pattern forming method) of the present embodiment is a step (B-1) of forming a lower layer film on a substrate using the lower layer film forming material (the composition of the present embodiment).
- the intermediate layer film is etched using the resist pattern as a mask
- the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask
- the substrate is etched using the obtained lower layer film pattern as an etching mask.
- the resist intermediate layer film material may contain silicon atoms.
- the formation method of the lower layer film for lithography in the present embodiment is not particularly limited as long as it is formed from the lower layer film forming material, and a known method can be applied.
- a known method such as spin coating or screen printing or a printing method, and removing the organic solvent by volatilizing the organic solvent
- the lower layer film material is crosslinked by a known method. And cured to form the lower layer film for lithography of the present embodiment.
- the crosslinking method include methods such as thermosetting and photocuring.
- the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ° C., more preferably 200 to 400 ° C.
- the baking time is not particularly limited, but is preferably within the range of 10 to 300 seconds.
- the thickness of the lower layer film can be appropriately selected according to the required performance and is not particularly limited, but is usually preferably about 30 to 20,000 nm, more preferably 50 to 15,000 nm. It is preferable.
- a silicon-containing resist layer is formed thereon, or a single-layer resist made of ordinary hydrocarbons.
- a silicon-containing intermediate layer is formed thereon, and further thereon. It is preferable to produce a single-layer resist layer that does not contain silicon. In this case, a well-known thing can be used as a photoresist material for forming this resist layer.
- a silicon-containing resist layer or a single layer resist made of ordinary hydrocarbon can be formed on the lower layer film.
- a silicon-containing intermediate layer can be formed on the lower layer film, and a single-layer resist layer not containing silicon can be formed on the silicon-containing intermediate layer.
- the photoresist material for forming the resist layer can be appropriately selected from known materials and is not particularly limited.
- a silicon-containing resist material for a two-layer process from the viewpoint of oxygen gas etching resistance, a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as a base polymer, and an organic solvent, an acid generator, If necessary, a positive photoresist material containing a basic compound or the like is preferably used.
- a silicon atom-containing polymer a known polymer used in this type of resist material can be used.
- a polysilsesquioxane-based intermediate layer is preferably used as the silicon-containing intermediate layer for the three-layer process.
- the intermediate layer By giving the intermediate layer an effect as an antireflection film, reflection tends to be effectively suppressed.
- the k value increases and the substrate reflection tends to increase, but the reflection is suppressed in the intermediate layer.
- the substrate reflection can be reduced to 0.5% or less.
- the intermediate layer having such an antireflection effect is not limited to the following, but for 193 nm exposure, a polysilsesquioxy crosslinked with acid or heat into which a light absorbing group having a phenyl group or a silicon-silicon bond is introduced. Sun is preferably used.
- an intermediate layer formed by a chemical vapor deposition (CVD) method can also be used.
- the intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, but for example, a SiON film is known.
- the formation of the intermediate layer by a wet process such as spin coating or screen printing has a simpler and more cost-effective advantage than the CVD method.
- the upper layer resist in the three-layer process may be either a positive type or a negative type, and the same one as a commonly used single layer resist can be used.
- the lower layer film in this embodiment can also be used as an antireflection film for a normal single layer resist or a base material for suppressing pattern collapse. Since the lower layer film of this embodiment is excellent in etching resistance for the base processing, it can be expected to function as a hard mask for the base processing.
- a wet process such as spin coating or screen printing is preferably used as in the case of forming the lower layer film.
- prebaking is usually performed, but this prebaking is preferably performed at 80 to 180 ° C. for 10 to 300 seconds.
- a resist pattern can be obtained by performing exposure, post-exposure baking (PEB), and development.
- the thickness of the resist film is not particularly limited, but is generally preferably 30 to 500 nm, more preferably 50 to 400 nm.
- the exposure light may be appropriately selected and used according to the photoresist material to be used.
- high energy rays having a wavelength of 300 nm or less, specifically, 248 nm, 193 nm, 157 nm excimer laser, 3 to 20 nm soft X-ray, electron beam, X-ray and the like can be mentioned.
- the resist pattern formed by the above-described method is one in which pattern collapse is suppressed by the lower layer film in the present embodiment. Therefore, by using the lower layer film in the present embodiment, a finer pattern can be obtained, and the exposure amount necessary for obtaining the resist pattern can be reduced.
- gas etching is preferably used as the etching of the lower layer film in the two-layer process.
- gas etching etching using oxygen gas is suitable.
- an inert gas such as He or Ar, or CO, CO 2 , NH 3 , SO 2 , N 2 , NO 2 or H 2 gas may be added.
- gas etching can be performed only with CO, CO 2 , NH 3 , N 2 , NO 2, and H 2 gas without using oxygen gas.
- the latter gas is preferably used for side wall protection for preventing undercut of the pattern side wall.
- gas etching is also preferably used for etching the intermediate layer in the three-layer process.
- the gas etching the same gas etching as described in the above two-layer process can be applied.
- the processing of the intermediate layer in the three-layer process is preferably performed using a fluorocarbon gas and a resist pattern as a mask.
- the lower layer film can be processed by, for example, oxygen gas etching using the intermediate layer pattern as a mask.
- a silicon oxide film, a silicon nitride film, or a silicon oxynitride film is formed by a CVD method, an ALD method, or the like.
- the method for forming the nitride film is not limited to the following, but for example, the method described in Japanese Patent Application Laid-Open No. 2002-334869 (the above-mentioned Patent Document 6) and WO 2004/066377 (the above-mentioned Patent Document 7) is used. it can.
- a photoresist film can be formed directly on such an intermediate film, but an organic antireflection film (BARC) is formed on the intermediate film by spin coating, and a photoresist film is formed thereon. May be.
- BARC organic antireflection film
- an intermediate layer based on polysilsesquioxane is also preferably used.
- the resist intermediate layer film By providing the resist intermediate layer film with an effect as an antireflection film, reflection tends to be effectively suppressed.
- Specific materials of the polysilsesquioxane-based intermediate layer are not limited to the following, but examples thereof include Japanese Patent Application Laid-Open No. 2007-226170 (the above-mentioned Patent Document 8) and Japanese Patent Application Laid-Open No. 2007-226204 (the above-mentioned Patent Document). Those described in 9) can be used.
- Etching of the next substrate can also be performed by a conventional method.
- the substrate is SiO 2 or SiN
- etching mainly using a chlorofluorocarbon gas if p-Si, Al, or W is chlorine or bromine, Etching mainly with gas can be performed.
- the substrate is etched with a chlorofluorocarbon gas, the silicon-containing resist of the two-layer resist process and the silicon-containing intermediate layer of the three-layer process are peeled off simultaneously with the substrate processing.
- the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled, and generally, dry etching peeling with a chlorofluorocarbon-based gas is performed after the substrate is processed. .
- the lower layer film is characterized by excellent etching resistance of these substrates.
- a known substrate can be appropriately selected and used, and is not particularly limited. Examples thereof include Si, ⁇ -Si, p-Si, SiO 2 , SiN, SiON, W, TiN, and Al. .
- the substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). Examples of such processed films include various low-k films such as Si, SiO 2 , SiON, SiN, p-Si, ⁇ -Si, W, W-Si, Al, Cu, and Al-Si, and their stopper films. In general, a material different from the base material (support) is used.
- the thickness of the substrate to be processed or the film to be processed is not particularly limited, but is usually preferably about 50 to 10,000 nm, more preferably 75 to 5,000 nm.
- the resist permanent film which can produce a resist permanent film using the said composition is a permanent film which remains also in the final product after forming a resist pattern as needed. It is suitable as.
- the permanent film include a solder resist, a package material, an underfill material, a package adhesive layer such as a circuit element, an adhesive layer between an integrated circuit element and a circuit board, and a thin film display protective film for a thin display. Examples include a liquid crystal color filter protective film, a black matrix, and a spacer.
- the permanent film made of the above composition has excellent heat resistance and moisture resistance, and also has a very excellent advantage of less contamination due to sublimation components.
- a display material is a material having high sensitivity, high heat resistance, and moisture absorption reliability with little image quality deterioration due to important contamination.
- composition When the composition is used for a resist permanent film, other additives such as other resins, surfactants and dyes, fillers, cross-linking agents, and dissolution accelerators are added in addition to the curing agent. By dissolving in an organic solvent, a resist permanent film composition can be obtained.
- the film forming composition for lithography and the composition for resist permanent film can be prepared by blending the above components and mixing them using a stirrer or the like. Further, when the resist underlayer film composition or resist permanent film composition contains a filler or a pigment, it is adjusted by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill. I can do it.
- a dispersing device such as a dissolver, a homogenizer, or a three-roll mill. I can do it.
- Carbon concentration and oxygen concentration were measured by organic elemental analysis using the following apparatus.
- Apparatus CHN coder MT-6 (manufactured by Yanaco Analytical Industries)
- the molecular weight of the compound was measured by LC-MS analysis using Water's Acquity UPLC / MALDI-Synapt HDMS. Moreover, the gel permeation chromatography (GPC) analysis was performed on the following conditions, and the polystyrene conversion weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) were calculated
- Apparatus Shodex GPC-101 (manufactured by Showa Denko KK) Column: KF-80M x 3 Eluent: THF 1mL / min Temperature: 40 ° C
- the obtained resin (R1-BiP-1) had Mn: 1875, Mw: 3550, and Mw / Mn: 1.89.
- the obtained resin (R2-BiP-1) was Mn: 1682, Mw: 2910, and Mw / Mn: 1.73.
- the thermal decomposition temperature was 375 ° C. and the glass transition point was 80 ° C., confirming high heat resistance.
- the thermal decomposition temperature was 380 ° C. and the glass transition point was 90 ° C., confirming high heat resistance.
- the obtained resin (E-R1-BiP-1) had Mn: 2476, Mw: 4542, and Mw / Mn: 1.83.
- the obtained resin (G-R1-BiP-1) had Mn: 2799, Mw: 4982, and Mw / Mn: 1.78.
- the obtained resin (GE-R1-BiP-1) had Mn: 3216, Mw: 5845, and Mw / Mn: 1.82.
- the obtained resin (E-R2-BiP-1) was Mn: 2649, Mw: 4531, and Mw / Mn: 1.71.
- the obtained resin (G-R2-BiP-1) had Mn: 2630, Mw: 4682, and Mw / Mn: 1.78.
- the obtained resin (GE-R1-BiP-1) was Mn: 2712, Mw: 5641, and Mw / Mn: 2.08.
- ethylbenzene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Further, neutralization and washing with water were performed, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a light brown solid dimethylnaphthalene formaldehyde resin. The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562.
- a four-necked flask having an internal volume of 0.5 L equipped with a Dimroth condenser, a thermometer, and a stirring blade was prepared.
- This four-necked flask was charged with 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of paratoluenesulfonic acid in a nitrogen stream, and the temperature was raised to 190 ° C. Stir after heating for hours. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was further raised to 220 ° C. to react for 2 hours.
- the obtained resin (CR-1) was Mn: 885, Mw: 2220, and Mw / Mn: 4.17.
- materials for forming a lower layer film for lithography having the compositions shown in Table 6 below were prepared.
- these lower-layer film forming materials for lithography were spin-coated on a silicon substrate, and then baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to prepare 200 nm-thick underlayer films.
- the following were used about the acid generator, the crosslinking agent, and the organic solvent.
- Acid generator Ditertiary butyl diphenyliodonium nonafluoromethanesulfonate (DTDDPI) manufactured by Midori Chemical Co., Ltd.
- Crosslinking agent Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
- Organic solvent Propylene glycol monomethyl ether acetate acetate (PGMEA)
- Novolac PSM4357 manufactured by Gunei Chemical Co., Ltd.
- materials for forming a lower layer film for lithography having the compositions shown in Table 7 below were prepared.
- these lower layer film forming materials for lithography are spin-coated on a silicon substrate, and then baked at 110 ° C. for 60 seconds to remove the solvent of the coating film. Then, an integrated exposure amount of 600 mJ is obtained with a high-pressure mercury lamp. / cm 2, and is cured by irradiation time of 20 seconds to produce each an underlying film having a thickness of 200 nm.
- the photo acid generator, the crosslinking agent, and the organic solvent described in Table 6 were used.
- Photo acid generator WPA Pure Chemicals WPAG-336 (diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate) ⁇
- Crosslinking agent Diallyl bisphenol A cyanate manufactured by Mitsubishi Gas Chemical (DABPA-CN) Konishi Chemical Industry Diallylbisphenol A (BPA-CA) Benzoxazine (BF-BXZ) manufactured by Konishi Chemical Industries Nippon Kayaku Biphenyl Aralkyl Epoxy Resin (NC-3000-L) ⁇
- Organic solvent Propylene glycol monomethyl ether acetate acetate (PGMEA)
- the structure of the crosslinking agent is shown by the following formula.
- Etching system “RIE-10NR” manufactured by Samco International Output: 50W Pressure: 20Pa Time: 2min Etching gas
- Ar gas flow rate: CF 4 gas flow rate: O 2 gas flow rate 50: 5: 5 (sccm)
- Etching resistance was evaluated according to the following procedure. First, novolak was used under the same conditions as in Example 1-1 except that novolak (“PSM4357” manufactured by Gunei Chemical Co., Ltd.) was used instead of the compound (E-BiN-1) used in Example 1-1. A lower layer film was produced. And the above-mentioned etching test was done for the lower layer film of this novolak, and the etching rate at that time was measured.
- the above-mentioned etching test was similarly performed for the lower layer films of the examples and comparative examples, and the etching rate at that time was measured. Then, the etching resistance was evaluated according to the following evaluation criteria based on the etching rate of the novolak underlayer film.
- each solution of an underlayer film forming material for lithography containing E-BiN-1, E-BiP-1, G-BiN-1, G-BiP-1, GE-BiN-1, and GE-BiP-1
- the coating was applied on a SiO 2 substrate having a thickness of 300 nm and baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to form a lower layer film having a thickness of 70 nm.
- an ArF resist solution was applied and baked at 130 ° C. for 60 seconds to form a 140 nm-thick photoresist layer.
- the compound of the following formula (11) was prepared as follows. First, 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy- ⁇ -butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, 0.38 g of azobisisobutyronitrile, tetrahydrofuran The reaction solution was dissolved in 80 mL. This reaction solution was polymerized for 22 hours under a nitrogen atmosphere while maintaining the reaction temperature at 63 ° C., and then the reaction solution was dropped into 400 mL of n-hexane. The product resin thus obtained was coagulated and purified, and the resulting white powder was filtered and obtained by drying overnight at 40 ° C. under reduced pressure.
- the photoresist layer was exposed using an electron beam drawing apparatus (ELIONX, ELS-7500, 50 keV), baked at 115 ° C. for 90 seconds (PEB), and 2.38 mass% tetramethylammonium hydroxide (A positive resist pattern was obtained by developing with an aqueous solution of TMAH for 60 seconds.
- ELIONX electron beam drawing apparatus
- ELS-7500 ELS-7500, 50 keV
- PEB baked at 115 ° C. for 90 seconds
- TMAH 2.38 mass% tetramethylammonium hydroxide
- the shapes of the obtained resist patterns of 55 nm L / S (1: 1) and 80 nm L / S (1: 1) were observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd.
- S-4800 electron microscope
- the resist pattern was evaluated as “good” when the pattern was not collapsed and the rectangularity was good, and “bad”.
- the minimum line width with no pattern collapse and good rectangularity was used as an evaluation index as “resolution”.
- the minimum electron beam energy amount capable of drawing a good pattern shape was defined as “sensitivity” and used as an evaluation index. The results are shown in Table 8.
- Example 54 to 59 A solution of the material for forming a lower layer film for lithography of Examples 1-1 to 2-3 was applied on a SiO 2 substrate having a film thickness of 300 nm, and baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds. A lower layer film having a thickness of 80 nm was formed. On this lower layer film, a silicon-containing intermediate layer material was applied and baked at 200 ° C. for 60 seconds to form an intermediate layer film having a thickness of 35 nm. Further, the ArF resist solution was applied on this intermediate layer film and baked at 130 ° C. for 60 seconds to form a 150 nm-thick photoresist layer. As the silicon-containing intermediate layer material, a silicon atom-containing polymer described in JP-A-2007-226170 ⁇ Synthesis Example 1> was used.
- the photoresist layer was subjected to mask exposure using an electron beam lithography apparatus (ELIONX, ELS-7500, 50 keV), baked at 115 ° C. for 90 seconds (PEB), and 2.38 mass% tetramethylammonium hydroxide.
- ELIONX electron beam lithography apparatus
- PEB baked at 115 ° C. for 90 seconds
- TMAH tetramethylammonium hydroxide
- an optical component-forming composition was prepared with the formulation shown in Table 9 below.
- the following were used for the acid generator, crosslinking agent, acid diffusion inhibitor, and solvent.
- Acid generator Ditertiary butyl diphenyliodonium nonafluoromethanesulfonate (DTDDPI) manufactured by Midori Chemical Co., Ltd.
- Crosslinking agent Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
- Organic solvent Propylene glycol monomethyl ether acetate acetate (PGMEA)
- PMEA Propylene glycol monomethyl ether acetate acetate
- the optical component-forming composition in a uniform state was spin-coated on a clean silicon wafer, and then pre-baked (PB) in an oven at 110 ° C. to form an optical component-forming film having a thickness of 1 ⁇ m.
- the prepared optical component-forming composition was evaluated as “A” when the film formation was good and “C” when the formed film had defects.
- a uniform optical component-forming composition was spin-coated on a clean silicon wafer, and then PB was performed in an oven at 110 ° C. to form a film having a thickness of 1 ⁇ m.
- a resist composition was prepared according to the formulation shown in Table 10 below.
- the following were used for the acid generator, crosslinking agent, acid diffusion inhibitor, and solvent.
- Acid generator Triphenylphosphonium trifluoromethanesulfonate manufactured by Midori Kagaku Co., Ltd.
- Crosslinking agent Nicalak MX270 manufactured by Sanwa Chemical Co., Ltd.
- Acid diffusion inhibitor Trioctylamine manufactured by Tokyo Chemical Industry Co., Ltd.
- Organic solvent Propylene glycol monomethyl ether (PGME) manufactured by Tokyo Chemical Industry Co., Ltd.
- the line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation), and the reactivity of the resist composition by electron beam irradiation was evaluated.
- Sensitivity was expressed as the minimum amount of energy per unit area necessary for obtaining a pattern, and was evaluated according to the following.
- the obtained pattern shape is transferred to an SEM (Scanning Electron Microscope). And evaluated according to the following.
- C When a non-rectangular pattern is obtained
- the compound and resin of this embodiment have high solubility in a safe solvent, good heat resistance and etching resistance, and the resist composition provides a good resist pattern shape.
- a wet process can be applied, and a compound, a resin, and a film forming composition for lithography useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance can be realized.
- this film-forming composition for lithography uses a compound or resin having a specific structure that has high heat resistance and high solvent solubility, deterioration of the film during high-temperature baking is suppressed, oxygen plasma etching, etc. It is possible to form a resist and an underlayer film that are also excellent in etching resistance to.
- the adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed. Furthermore, since the refractive index is high and coloring is suppressed by low-temperature to high-temperature treatment, it is useful as various optical component-forming compositions.
- the present invention provides, for example, an electrical insulating material, a resist resin, a semiconductor sealing resin, an adhesive for a printed wiring board, an electrical laminate mounted on an electrical device / electronic device / industrial device, etc. ⁇ Matrix resin for prepregs, built-up laminate materials, resin for fiber reinforced plastics, sealing resin for liquid crystal display panels, paints, various coating agents, adhesives, and coatings for semiconductors installed in electronic equipment and industrial equipment
- resin resist resin for semiconductors, resin for forming lower layer film, film and sheet, plastic lens (prism lens, lenticular lens, micro lens, Fresnel lens, viewing angle control lens, contrast enhancement lens, etc.) , Retardation film, electromagnetic shielding film, prism, optical fiber, flexible Solder resist printed wiring, plating resist, multilayer printed wiring boards interlayer insulating film, the optical component such as a photosensitive optical waveguide, it is widely and effectively available.
- the present invention can be used particularly effectively in the fields of lithography resists, lithography resists,
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Abstract
Description
そこで、これまでに、より解像性の高いレジストパターンを与えるために、種々の低分子量レジスト材料が提案されている。低分子量レジスト材料は分子サイズが小さいことから、解像性が高く、ラフネスが小さいレジストパターンを与えることが期待される。
さらに、従来数多くの光学部材向け組成物が提案されているが、耐熱性、透明性及び屈折率を高い次元で両立させたものはなく、新たな材料の開発が求められている。
すなわち、本発明は、次のとおりである。
(式(0)中、RYは、炭素数1~30のアルキル基又は炭素数6~30のアリール基であり、
RZは、炭素数1~60のN価の基又は単結合であり、
RTは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、RTの少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
Xは、酸素原子、硫黄原子又は無架橋であることを表し、
mは、各々独立して0~9の整数であり、ここで、mの少なくとも1つは1~9の整数であり、
Nは、1~4の整数であり、Nが2以上の整数の場合、N個の[ ]内の構造式は同一であっても異なっていてもよく、
rは、各々独立して0~2の整数である。)
<2> 前記式(0)で表される化合物が下記式(1)で表される化合物である、前記<1>に記載の化合物。
(式(1)中、R0は、前記RYと同義であり、
R1は、炭素数1~60のn価の基又は単結合であり、
R2~R5は、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、R2~R5の少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
m2及びm3は、各々独立して、0~8の整数であり、
m4及びm5は、各々独立して、0~9の整数であり、
但し、m2、m3、m4及びm5は同時に0となることはなく、
nは前記Nと同義であり、ここで、nが2以上の整数の場合、n個の[ ]内の構造式は同一であっても異なっていてもよく、
p2~p5は、前記rと同義である。)
<3> 前記式(0)で表される化合物が下記式(2)で表される化合物である、前記<1>に記載の化合物。
(式(2)中、R0Aは、前記RYと同義であり、
R1Aは、炭素数1~60のnA価の基又は単結合であり、
R2Aは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、R2Aの少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
nAは、前記Nと同義であり、ここで、nAが2以上の整数の場合、nA個の[ ]内の構造式は同一であっても異なっていてもよく、
XAは、前記Xと同義あり、
m2Aは、各々独立して、0~7の整数であり、但し、少なくとも1つのm2Aは1~7の整数であり、
qAは、各々独立して、0又は1である。)
<4> 前記式(1)で表される化合物が下記式(1-1)で表される化合物である、前記<2>に記載の化合物。
(式(1-1)中、R0、R1、R4、R5、n、p2~p5、m4及びm5は、前記と同義であり、
R6~R7は、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基であり、
R10~R11は、各々独立して、水素原子又はヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基であり、
ここで、R10~R11の少なくとも1つはヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基から選ばれる1つの基であり、
m6及びm7は、各々独立して、0~7の整数であり、
但し、m4、m5、m6及びm7は同時に0となることはない。)
<5> 前記式(1-1)で表される化合物が下記式(1-2)で表される化合物である、前記<4>に記載の化合物。
(式(1-2)中、R0、R1、R6、R7、R10、R11、n、p2~p5、m6及びm7は、前記と同義であり、
R8~R9は、前記R6~R7と同義であり、
R12~R13は、前記R10~R11と同義であり、
m8及びm9は、各々独立して、0~8の整数であり、
但し、m6、m7、m8及びm9は同時に0となることはない。)
<6> 前記式(2)で表される化合物が下記式(2-1)で表される化合物である、前記<3>に記載の化合物。
(式(2-1)中、R0A、R1A、nA、qA及びXA、は、前記式(2)で説明したものと同義である。
R3Aは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基であり、
R4Aは、各々独立して、水素原子又はヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基であり、
ここで、R4Aの少なくとも1つはヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基であり、
m6Aは、各々独立して、0~5の整数である。)
<7> 前記<1>に記載の化合物をモノマーとして得られる、樹脂。
<8> 下記式(3)で表される構造を有する、前記<7>に記載の樹脂。
(式(3)中、
Lは、置換基を有していてもよい炭素数1~30のアルキレン基、置換基を有していてもよい炭素数6~30のアリーレン基、置換基を有していてもよい炭素数1~30のアルコキシレン基又は単結合であり、前記アルキレン基、前記アリーレン基、前記アルコキシレン基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、
R0は、前記RYと同義であり、
R1は、炭素数1~60のn価の基又は単結合であり、
R2~R5は、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、m2及びm3は、各々独立して、0~8の整数であり、
m4及びm5は、各々独立して、0~9の整数であり、
但し、m2、m3、m4及びm5は同時に0となることはなく、R2~R5の少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基である。
nは前記Nと同義であり、ここで、nが2以上の整数の場合、n個の[ ]内の構造式は同一であっても異なっていてもよく、
p2~p5は、前記rと同義である。)
<9> 下記式(4)で表される構造を有する、前記<7>に記載の樹脂。
(式(4)中、Lは、置換基を有していてもよい炭素数1~30のアルキレン基、置換基を有していてもよい炭素数6~30のアリーレン基、置換基を有していてもよい炭素数1~30のアルコキシレン基又は単結合であり、前記アルキレン基、前記アリーレン基、前記アルコキシレン基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、
R0Aは、前記RYと同義であり、
R1Aは、炭素数1~30のnA価の基又は単結合であり、
R2Aは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、R2Aの少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
nAは、前記Nと同義であり、ここで、nAが2以上の整数の場合、nA個の[ ]内の構造式は同一であっても異なっていてもよく、
XAは、前記Xと同義あり、
m2Aは、各々独立して、0~7の整数であり、但し、少なくとも1つのm2Aは1~6の整数であり、
qAは、各々独立して、0又は1である。)
<10> 前記<1>~<6>のいずれか一つに記載の化合物及び前記<7>~<9>のいずれか一つに記載の樹脂からなる群より選ばれる1種以上を含有する、組成物。
<11> 溶媒をさらに含有する、前記<10>に記載の組成物。
<12> 酸発生剤をさらに含有する、前記<10>又は前記<11>に記載の組成物。
<13> 架橋剤をさらに含有する、前記<10>~<12>のいずれか一つに記載の組成物。
<14> 前記架橋剤が、フェノール化合物、エポキシ化合物、シアネート化合物、アミノ化合物、ベンゾオキサジン化合物、メラミン化合物、グアナミン化合物、グリコールウリル化合物、ウレア化合物、イソシアネート化合物及びアジド化合物からなる群より選ばれる少なくとも1種である、前記<13>に記載の組成物。
<15> 前記架橋剤が、少なくとも1つのアリル基を有する、前記<13>又は<14>に記載の組成物。
<16> 前記架橋剤の含有量が、前記<1>~<6>のいずれか一つに記載の化合物及び前記<7>~<9>のいずれか一つに記載の樹脂からなる群より選ばれる1種以上を含有する組成物の合計質量100質量部に対し、0.1~100質量部である、前記<13>~<15>のいずれか一つに記載の組成物。
<17> 架橋促進剤をさらに含有する、前記<13>~<16>のいずれか一つに記載の組成物。
<18> 前記架橋促進剤が、アミン類、イミダゾール類、有機ホスフィン類、及びルイス酸からなる群より選ばれる少なくとも1種である、前記<17>に記載の組成物。
<19> 前記架橋促進剤の含有量が、前記<1>~<6>のいずれか一つに記載の化合物及び前記<7>~<9>のいずれか一つに記載の樹脂からなる群より選ばれる1種以上を含有する組成物の合計質量100質量部に対し、0.1~5質量部である、前記<17>又は<18>に記載の組成物。
<20> ラジカル重合開始剤をさらに含有する、前記<10>~<19>のいずれか一つに記載の組成物。
<21> 前記ラジカル重合開始剤が、ケトン系光重合開始剤、有機過酸化物系重合開始剤及びアゾ系重合開始剤からなる群より選ばれる少なくとも1種である、前記<10>~<20>のいずれか一つに記載の組成物。
<22> 前記ラジカル重合開始剤の含有量が、前記<1>~<6>のいずれか一つに記載の化合物及び前記<7>~<9>のいずれか一項に記載の樹脂からなる群より選ばれる1種以上を含有する組成物の合計質量100質量部に対し、0.05~25質量部である、前記<10>~<21>のいずれか一つに記載の組成物。
<23> リソグラフィー用膜形成に用いられる、前記<10>~<22>のいずれか一つに記載の組成物。
<24> レジスト永久膜形成に用いられる、前記<10>~<22>のいずれか一つに記載の組成物。
<25> 光学部品形成に用いられる、前記<10>~<22>のいずれか一つに記載の組成物。
<26> 基板上に、前記<23>に記載の組成物を用いてフォトレジスト層を形成した後、前記フォトレジスト層の所定の領域に放射線を照射し、現像を行う工程を含む、レジストパターン形成方法。
<27> 基板上に、前記<23>に記載の組成物を用いて下層膜を形成し、前記下層膜上に、少なくとも1層のフォトレジスト層を形成した後、前記フォトレジスト層の所定の領域に放射線を照射し、現像を行う工程を含む、レジストパターン形成方法。
<28> 基板上に、前記<23>に記載の組成物を用いて下層膜を形成し、前記下層膜上に、レジスト中間層膜材料を用いて中間層膜を形成し、前記中間層膜上に、少なくとも1層のフォトレジスト層を形成した後、前記フォトレジスト層の所定の領域に放射線を照射し、現像してレジストパターンを形成し、その後、前記レジストパターンをマスクとして前記中間層膜をエッチングし、得られた中間層膜パターンをエッチングマスクとして前記下層膜をエッチングし、得られた下層膜パターンをエッチングマスクとして基板をエッチングすることにより基板にパターンを形成する工程を含む、回路パターン形成方法。
本実施形態の化合物は後述の式(0)で表される化合物、又は、当該化合物をモノマーとして得られる樹脂である。本実施形態の化合物及び樹脂は、湿式プロセスが適用可能であり、耐熱性、安全溶媒に対する溶解性及びエッチング耐性に優れるフォトレジスト及びフォトレジスト用下層膜を形成するために有用であり、リソグラフィー用膜形成に有用な組成物及び該組成物を用いたパターン形成方法等に用いることができる。また、本実施形態の化合物及び樹脂は、感光性材料に用いた際の感度や解像度に優れるものであり、耐熱性の高さを維持しつつ、更に、汎用有機溶剤や他の化合物、樹脂成分、および添加剤との相溶性に優るレジスト永久膜を形成するために有用である。
上述の組成物は、耐熱性が高く、溶媒溶解性も高い、特定構造を有する化合物又は樹脂を用いているため、高温ベーク時の膜の劣化が抑制され、酸素プラズマエッチング等に対するエッチング耐性にも優れたレジスト及び下層膜を形成することができる。加えて、下層膜を形成した場合、レジスト層との密着性にも優れるので、優れたレジストパターンを形成することができる。
さらに、上述の組成物は、屈折率が高く、また低温から高温までの広範囲の熱処理によって着色が抑制されることから、各種光学形成組成物としても有用である。
本実施形態の化合物は、下記式(0)で表される。
(式(0)中、RYは、炭素数1~30のアルキル基又は炭素数6~30のアリール基であり、
RZは、炭素数1~60のN価の基又は単結合であり、
RTは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、RTの少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
Xは、酸素原子、硫黄原子又は無架橋であることを表し、
mは、各々独立して0~9の整数であり、ここで、mの少なくとも1つは1~9の整数であり、
Nは、1~4の整数であり、Nが2以上の整数の場合、N個の[ ]内の構造式は同一であっても異なっていてもよく、
rは、各々独立して0~2の整数である。)
またRYが、炭素数1~30の直鎖状、分岐状若しくは環状のアルキル基又は炭素数6~30のアリール基であると、更に、本化合物の酸化分解を抑制し着色を抑え、耐熱性が高く、溶媒溶解性を向上させる観点から好ましい。
ここで、「水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基」とは、水酸基の水素原子がヒドロキシアルキル基で置換された基、及び、水酸基の水素原子がグリシジル基で置換された基の他に、水酸基の水素原子がヒドロキシアルキル基で置換され、更に当該ヒドロキシアルキル基の水酸基(ヒドロキシ基)が他の置換基で置換された基も含む。前記ヒドロキシアルキル基の水酸基が他の置換基で置換された基は、特に限定されるものではないが、例えば、前記水酸基がグリシジル基で置換されたグリシジルオキシアルキル基等が挙げられる。また、前記ヒドロキシアルキル基中のアルキル基は特に限定されるものではないが、例えば、メチル基、エチル基、プロピル基等が挙げられる。更に、後述のように、前記ヒドロキシアルキル基及びグリシジル基は、他の結合基を介して水酸基の水素原子に置換されていてもよい。前記他の結合基としては、例えば、酸素原子、アルキレン基やオキシアルキレン基等が挙げられる。
式(0)中、ナフタレン構造で示される部位は、r=0の場合には単環構造であり、r=1の場合には二環構造であり、r=2の場合には三環構造となる。rは、各々独立して0~2の整数である。上述のmは、rで決定される環構造に応じてその数値範囲が決定される。
本実施形態の化合物は、下記式(1)で表されることが好ましい。式(1)で表される化合物は、下記のように構成されているため、耐熱性が高く、溶媒溶解性も高い。
(式(1)中、R0は、前記RYと同義であり、
R1は、炭素数1~60のn価の基又は単結合であり、
R2~R5は、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、R2~R5の少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
m2及びm3は、各々独立して、0~8の整数であり、
m4及びm5は、各々独立して、0~9の整数であり、
但し、m2、m3、m4及びm5は同時に0となることはなく、
nは前記Nと同義であり、ここで、nが2以上の整数の場合、n個の[ ]内の構造式は同一であっても異なっていてもよく、
p2~p5は、前記rと同義である。)
R1は炭素数1~60のn価の基又は単結合であり、このR1を介して各々の芳香環が結合している。nは前記Nと同義であり、nが2以上の整数の場合、n個の[ ]内の構造式は同一であっても異なっていてもよい。なお、前記n価の基とは、n=1のときには、炭素数1~60のアルキル基、n=2のときには、炭素数1~30のアルキレン基、n=3のときには、炭素数2~60のアルカンプロパイル基、n=4のときには、炭素数3~60のアルカンテトライル基のことを示す。前記n価の基としては、例えば、直鎖状炭化水素基、分岐状炭化水素基又は脂環式炭化水素基を有するもの等が挙げられる。ここで、前記脂環式炭化水素基については、有橋脂環式炭化水素基も含まれる。また、前記n価の炭化水素基は、脂環式炭化水素基、二重結合、ヘテロ原子もしくは炭素数6~60の芳香族基を有していてもよい。
尚、前記アルキル基、アルケニル基及びアルコキシ基は、直鎖状、分岐状若しくは環状の基であってもよい。
ここで、R10~R11の少なくとも1つはヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基であり、m6及びm7は、各々独立して0~7の整数である。但し、m4、m5、m6及びm7は同時に0となることはない。
但し、R2、R3、R4、R5から選ばれる少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、m2、m3、m4、m5が同時に0となることはない。
但し、R2、R3、R4、R5から選ばれる少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、m2、m3、m4、m5が同時に0となることはない。
但し、R2、R3、R4、R5から選ばれる少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、m2、m3、m4、m5が同時に0となることはない。
但し、R2、R3、R4、R5から選ばれる少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、m2、m3、m4、m5が同時に0となることはない。
R0は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリアコンチル基、フェニル基、ナフチル基、アントラセン基、ピレニル基、ビフェニル基、ヘプタセン基が挙げられる。
R4'及びR5'は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリアコンチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基、シクロトリアコンチル基、ノルボルニル基、アダマンチル基、フェニル基、ナフチル基、アントラセン基、ピレニル基、ビフェニル基、ヘプタセン基、ビニル基、アリル基、トリアコンテニル基、メトキシ基、エトキシ基、トリアコンチキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、チオール基が挙げられる。
前記R0、R4'、R5'の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
前記R16の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
R14は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリアコンチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基、シクロトリアコンチル基、ノルボルニル基、アダマンチル基、フェニル基、ナフチル基、アントラセン基、ピレニル基、ビフェニル基、ヘプタセン基、ビニル基、アリル基、トリアコンテニル基、メトキシ基、エトキシ基、トリアコンチキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、チオール基が挙げられる。
前記R14の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
R14は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリアコンチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基、シクロトリアコンチル基、ノルボルニル基、アダマンチル基、フェニル基、ナフチル基、アントラセン基、ピレニル基、ビフェニル基、ヘプタセン基、ビニル基、アリル基、トリアコンテニル基、メトキシ基、エトキシ基、トリアコンチキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、チオール基が挙げられる。
前記R14の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
R15は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリアコンチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基、シクロトリアコンチル基、ノルボルニル基、アダマンチル基、フェニル基、ナフチル基、アントラセン基、ピレニル基、ビフェニル基、ヘプタセン基、ビニル基、アリル基、トリアコンテニル基、メトキシ基、エトキシ基、トリアコンチキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、チオール基が挙げられる。
前記R15の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
R14は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリアコンチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基、シクロトリアコンチル基、ノルボニル基、アダマンチル基、フェニル基、ナフチル基、アントラセン基、ヘプタセン基、ビニル基、アリル基、トリアコンテニル基、メトキシ基、エトキシ基、トリアコンチキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、チオール基が挙げられる。
前記R14の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
R15は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリアコンチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基、シクロトリアコンチル基、ノルボニル基、アダマンチル基、フェニル基、ナフチル基、アントラセン基、ヘプタセン基、ビニル基、アリル基、トリアコンテニル基、メトキシ基、エトキシ基、トリアコンチキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、チオール基が挙げられる。
前記R15の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
R16は、例えば、メチレン基、エチレン基、プロペン基、ブテン基、ペンテン基、ヘキセン基、ヘプテン基、オクテン基、ノネン基、デセン基、ウンデセン基、ドデセン基、トリアコンテン基、シクロプロペン基、シクロブテン基、シクロペンテン基、シクロヘキセン基、シクロヘプテン基、シクロオクテン基、シクロノネン基、シクロデセン基、シクロウンデセン基、シクロドデセン基、シクロトリアコンテン基、2価のノルボニル基、2価のアダマンチル基、2価のフェニル基、2価のナフチル基、2価のアントラセン基、2価のヘプタセン基、2価のビニル基、2価のアリル基、2価のトリアコンテニル基が挙げられる。
前記R16の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
R14は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリアコンチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基、シクロトリアコンチル基、ノルボニル基、アダマンチル基、フェニル基、ナフチル基、アントラセン基、ヘプタセン基、ビニル基、アリル基、トリアコンテニル基、メトキシ基、エトキシ基、トリアコンチキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、チオール基が挙げられる。
前記R14の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
R14は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリアコンチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基、シクロトリアコンチル基、ノルボニル基、アダマンチル基、フェニル基、ナフチル基、アントラセン基、ヘプタセン基、ビニル基、アリル基、トリアコンテニル基、メトキシ基、エトキシ基、トリアコンチキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、チオール基が挙げられる。
前記R14の各例示は、異性体を含む。例えば、ブチル基には、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が含まれる。
前記列挙した化合物は、耐熱性の観点から、キサンテン骨格を有する化合物が好ましい。
本実施形態で使用される式(0)で表される化合物は、公知の手法を応用して適宜合成することができ、その合成手法は特に限定されない。例えば、式(1)で表される化合物を例にとると、式(0)で表される化合物は以下のように合成することができる。
例えば、式(1)で表される化合物は常圧下、ビフェノール類、ビナフトール類又はビアントラセンオール類と、対応するケトン類とを酸触媒下にて重縮合反応させることによりポリフェノール化合物を得て、続いて、ポリフェノール化合物の少なくとも1つのフェノール性水酸基に、ヒドロキシアルキル基又はグリシジル基を導入し、或いは、更にヒドロキシアルキル基のヒドロキシ基にグリシジル基を導入することにより得られる。また、前記合成は必要に応じて、加圧下で行うこともできる。
ヒドロキシアルキル基のヒドロキシ基にグリシジル基を導入するタイミングについては、ヒドロキシアルキル基を導入した後の段階であればよく、縮合反応の前段階、後段階、ヒドロキシアルキル基の導入反応の前段階、後段階又は後述する樹脂の製造を行なった後に行なってもよい。
例えば、以下のようにして、ポリフェノール化合物の少なくとも1つのフェノール性水酸基にヒドロキシアルキル基を導入することができる。
ヒドロキシアルキル基は、オキシアルキル基を介してフェノール性水酸基に導入されることもある。例えば、ヒドロキシアルキルオキシアルキル基やヒドロキシアルキルオキシアルキルオキシアルキル基が導入される。
ヒドロキシアルキル基を導入するための化合物は、公知の方法で合成もしくは容易に入手でき、例えば、クロロエタノール、ブロモエタノール、酢酸-2-クロロエチル、酢酸-2-ブロモエチル、酢酸-2-ヨードエチル、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネートが挙げられるが特に限定はされない。
また、例えば、酢酸-2-クロロエチル、酢酸-2-ブロモエチル、酢酸-2-ヨードエチルを使用する場合、アセトキシエチル基が導入されたのち、脱アシル反応を生じることにより、ヒドロキシエチル基が導入される。
また、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネートを使用する場合、アルキレンカーボネートを付加させ、脱炭酸反応が生じることにより、ヒドロキシアルキル基が導入される。
前記式(0)で表される化合物は、リソグラフィー用膜形成組成物として、そのまま使用することができる。また、前記式(0)で表される化合物をモノマーとして得られる樹脂としても使用することができる。換言すると、本実施形態の樹脂は前記一般式(0)に由来する単位構造を有する樹脂である。例えば、前記式(0)で表される化合物と架橋反応性のある化合物とを反応させて得られる樹脂としても使用することができる。
前記式(0)で表される化合物をモノマーとして得られる樹脂としては、例えば、以下の式(3)に表される構造を有するものが挙げられる。すなわち、本実施形態の組成物は、下記式(3)に表される構造を有する樹脂を含有するものであってもよい。
(式(3)中、Lは、置換基を有していてもよい炭素数1~30のアルキレン基、置換基を有していてもよい炭素数6~30のアリーレン基、置換基を有していてもよい炭素数1~30のアルコキシレン基又は単結合であり、前記アルキレン基、前記アリーレン基、前記アルコキシレン基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、
R0は、前記RYと同義であり、
R1は、炭素数1~60のn価の基又は単結合であり、
R2~R5は、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、m2及びm3は、各々独立して、0~8の整数であり、
m4及びm5は、各々独立して、0~9の整数であり、
但し、m2、m3、m4及びm5は同時に0となることはなく、R2~R5の少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基である。
nは前記Nと同義であり、ここで、nが2以上の整数の場合、n個の[ ]内の構造式は同一であっても異なっていてもよく、
p2~p5は、前記rと同義である。)
本実施形態の樹脂は、前記式(0)で表される化合物を架橋反応性のある化合物と反応させることにより得られる。架橋反応性のある化合物としては、前記式(0)で表される化合物をオリゴマー化又はポリマー化し得るものである限り、公知のものを特に制限なく使用することができる。その具体例としては、例えば、アルデヒド、ケトン、カルボン酸、カルボン酸ハライド、ハロゲン含有化合物、アミノ化合物、イミノ化合物、イソシアネート、不飽和炭化水素基含有化合物等が挙げられるが、これらに特に限定されない。
本実施形態の化合物は、下記式(2)で表されることも好ましい。式(2)で表される化合物は、以下のように構成されているため、耐熱性が高く、溶媒溶解性も高い。
(式(2)中、R0Aは、前記RYと同義であり、
R1Aは、炭素数1~60のnA価の基又は単結合であり、
R2Aは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、R2Aの少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
nAは、前記Nと同義であり、ここで、nAが2以上の整数の場合、nA個の[ ]内の構造式は同一であっても異なっていてもよく、
XAは、前記Xと同義あり、
m2Aは、各々独立して、0~7の整数であり、但し、少なくとも1つのm2Aは1~7の整数であり、
qAは、各々独立して、0又は1である。)
R1Aは、炭素数1~60のnA価の基又は単結合である。nAは前記Nと同義であり、1~4の整数である。式(2)中、nAが2以上の整数の場合、nA個の[ ]内の構造式は同一であっても異なっていてもよい。
なお、前記nA価の基とは、nA=1のときには、炭素数1~60のアルキル基、nA=2のときには、炭素数1~60のアルキレン基、nA=3のときには、炭素数2~60のアルカンプロパイル基、nA=4のときには、炭素数3~60のアルカンテトライル基のことを示す。前記n価の基としては、例えば、直鎖状炭化水素基、分岐状炭化水素基又は脂環式炭化水素基を有するもの等が挙げられる。ここで、前記脂環式炭化水素基については、有橋脂環式炭化水素基も含まれる。また、前記n価の炭化水素基は、脂環式炭化水素基、二重結合、ヘテロ原子もしくは炭素数6~60の芳香族基を有していてもよい。
R4Aは、各々独立して、水素原子又はヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基であり、ここで、R4Aの少なくとも1つはヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基であり、m6Aは、各々独立して、0~5の整数である。
本実施形態で使用される式(2)で表される化合物は、公知の手法を応用して適宜合成することができ、その合成手法は特に限定されない。
例えば、常圧下、フェノール類、ナフトール類と、対応するケトン類とを酸触媒下にて重縮合反応させることによりポリフェノール化合物を得て、続いて、ポリフェノール化合物の少なくとも1つのフェノール性水酸基に、ヒドロキシアルキル基又はグリシジル基を導入し、或いは、更にヒドロキシアルキル基のヒドロキシ基にグリシジル基を導入することにより得られる。
また、前記合成は必要に応じて、加圧下で行うこともできる。
ヒドロキシアルキル基のヒドロキシ基にグリシジル基を導入するタイミングについては、ヒドロキシアルキル基を導入した後段階であればよく、縮合反応の前段階、後段階、ヒドロキシアルキル基の導入反応の前段階、後段階又は後述する樹脂の製造を行なった後に行なってもよい。
ケトン類として、芳香環を有するケトンを用いることが、高い耐熱性及び高いエッチング耐性を兼備し好ましい。
前記ポリフェノール化合物を製造する際、反応温度は、特に限定されず、反応原料の反応性に応じて適宜選択することができるが、10~200℃の範囲であることが好ましい。本実施形態の式(2)で表される化合物を選択性よく合成するには、温度が低い方が、効果が高く10~60℃の範囲がより好ましい。
前記化合物の製造方法は、特に限定されないが、例えば、ナフトール類等、ケトン類、触媒を一括で仕込む方法や、触媒存在下ナフトール類やケトン類を滴下していく方法がある。重縮合反応終了後、系内に存在する未反応原料、触媒等を除去するために、反応釜の温度を130~230℃ にまで上昇させ、1~50mmHg程度で揮発分を除去することもできる。
例えば、以下のようにして、前記化合物の少なくとも1つのフェノール性水酸基にヒドロキシアルキル基を導入することができる。
ヒドロキシアルキル基は、オキシアルキル基を介してフェノール性水酸基に導入されることもある。例えば、ヒドロキシアルキルオキシアルキル基やヒドロキシアルキルオキシアルキルオキシアルキル基が導入される。
ヒドロキシアルキル基を導入するための化合物は、公知の方法で合成もしくは容易に入手でき、例えば、クロロエタノール、ブロモエタノール、酢酸-2-クロロエチル、酢酸-2-ブロモエチル、酢酸-2-ヨードエチル、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネートが挙げられるが特に限定はされない。
また、例えば、酢酸-2-クロロエチル、酢酸-2-ブロモエチル、酢酸-2-ヨードエチルを使用する場合、アセトキシエチル基が導入されたのち、脱アシル反応を生じることにより、ヒドロキシエチル基が導入される。
また、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネートを使用する場合、アルキレンカーボネートを付加させ、脱炭酸反応が生じることにより、ヒドロキシアルキル基が導入される。
前記式(2)で表される化合物は、リソグラフィー用膜形成組成物として、そのまま使用することができる。また、前記式(2)で表される化合物をモノマーとして得られる樹脂としても使用することができる。例えば、前記式(2)で表される化合物と架橋反応性のある化合物とを反応させて得られる樹脂としても使用することができる。
前記式(2)で表される化合物をモノマーとして得られる樹脂としては、例えば、以下の式(4)に表される構造を有するものが挙げられる。すなわち、本実施形態の組成物は、下記式(4)に表される構造を有する樹脂を含有するものであってもよい。
R0A、R1A、R2A、m2A、nA、qA及びXAは前記式(2)におけるものと同義であり、
nAが2以上の整数の場合、nA個の[ ]内の構造式は同一であっても異なっていてもよい。
但し、R2Aの少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含む。
前記式(0)で表される化合物及びこれをモノマーとして得られる樹脂は以下の精製方法によって精製ことができる。即ち、本実施形態の化合物及び/又は樹脂の精製方法は、前記式(0)で表される化合物及びこれをモノマーとして得られる樹脂(例えば、前記式(1)で表される化合物、前記式(1)で表される化合物をモノマーとして得られる樹脂、前記式(2)で表される化合物及び前記式(2)で表される化合物をモノマーとして得られる樹脂から選ばれる1種以上)を、溶媒に溶解させて溶液(S)を得る工程と、得られた溶液(S)と酸性の水溶液とを接触させて、前記化合物及び/又は前記樹脂中の不純物を抽出する工程(第一抽出工程)とを含み、前記溶液(S)を得る工程で用いる溶媒が、水と任意に混和しない有機溶媒を含む。
当該第一抽出工程において、前記樹脂は、例えば、前記式(1)で表される化合物及び/又は式(2)で表される化合物と架橋反応性のある化合物との反応によって得られる樹脂であることが好ましい。前記精製方法によれば、上述した特定の構造を有する化合物又は樹脂に不純物として含まれうる種々の金属の含有量を低減することができる。
より詳細には、前記精製方法においては、前記化合物及び/又は前記樹脂を、水と任意に混和しない有機溶媒に溶解させて溶液(S)を得て、さらにその溶液(S)を酸性水溶液と接触させて抽出処理を行うことができる。これにより、前記溶液(S)に含まれる金属分を水相に移行させたのち、有機相と水相とを分離して金属含有量の低減された化合物及び/又は樹脂を得ることができる。
また、ここで用いる水は、本実施の形態の目的に沿って、金属含有量の少ない水、例えば、イオン交換水等であることが好ましい。抽出処理は1回だけでもかまわないが、混合、静置、分離という操作を複数回繰り返して行うのも有効である。また、抽出処理における両者の使用割合や、温度、時間等の条件は特に限定されないが、先の酸性の水溶液との接触処理の場合と同様で構わない。
本実施形態の組成物は、上述の本実施形態の化合物及び樹脂からなる群より選ばれる1種以上を含有する。本実施形態の組成物は、溶媒、酸発生剤、架橋剤、架橋促進剤、ラジカル重合開始剤等を更に含有することができる。本実施形態の組成物は、リソグラフィー用膜形成用途(即ち、リソグラフィー用膜形成組成物)や光学部品形成用途に用いることができる。
本実施形態の組成物は、上述の本実施形態の化合物及び樹脂からなる群より選ばれる1種以上(例えば、前記式(1)で表される化合物、前記式(1)で表される化合物をモノマーとして得られる樹脂、前記式(2)で表される化合物及び前記式(2)で表される化合物をモノマーとして得られる樹脂からなる群より選ばれる1種以上)をレジスト基材として含有することができる。
本実施形態の組成物は化学増幅型レジスト用途向けリソグラフィー用膜形成組成物(以下、レジスト組成物とも称す)として用いることができる。レジスト組成物は、例えば、本実施形態の化合物及び樹脂からなる群より選ばれる1種以上を含有する。
前記レジスト組成物において、レジスト基材として用いる上述の本実施形態の化合物及び樹脂の含有量は、特に限定されないが、固形成分の全質量(レジスト基材、酸発生剤(C)、架橋剤(G)、酸拡散制御剤(E)及びその他の成分(F)などの任意に使用される成分を含む固形成分の総和、以下同様。)の50~99.4質量%であることが好ましく、より好ましくは55~90質量%、さらに好ましくは60~80質量%、特に好ましくは60~70質量%である。前記含有量の場合、解像度が一層向上し、ラインエッジラフネス(LER)が一層小さくなる。
なお、レジスト基材として化合物と樹脂の両方を含有する場合、前記含有量は、両成分の合計量である。
前記レジスト組成物には、本発明の目的を阻害しない範囲で、必要に応じて、レジスト基材、酸発生剤(C)、架橋剤(G)及び酸拡散制御剤(E)以外の成分として、溶解促進剤、溶解制御剤、増感剤、界面活性剤、有機カルボン酸又はリンのオキソ酸若しくはその誘導体、熱及び/又は光硬化触媒、重合禁止剤、難燃剤、充填剤、カップリング剤、熱硬化性樹脂、光硬化性樹脂、染料、顔料、増粘剤、滑剤、消泡剤、レベリング剤、紫外線吸収剤、界面活性剤、着色剤、ノニオン系界面活性剤等の各種添加剤を1種又は2種以上添加することができる。なお、本明細書において、その他の成分(F)を任意成分(F)ということがある。
好ましくは50~99.4/0.001~49/0.5~49/0.001~49/0~49、
より好ましくは55~90/1~40/0.5~40/0.01~10/0~5、
さらに好ましくは60~80/3~30/1~30/0.01~5/0~1、
特に好ましくは60~70/10~25/2~20/0.01~3/0、である。
各成分の配合割合は、その総和が100質量%になるように各範囲から選ばれる。前記配合にすると、感度、解像度、現像性等の性能に優れる。
前記レジスト組成物は、スピンコートによりアモルファス膜を形成することができる。また、一般的な半導体製造プロセスに適用することができる。上述の本実施形態の化合物及び樹脂の種類及び/又は用いる現像液の種類によって、ポジ型レジストパターン及びネガ型レジストパターンのいずれかを作り分けることができる。
ネガ型レジストパターンの場合、前記レジスト組成物をスピンコートして形成したアモルファス膜の23℃における現像液に対する溶解速度は、10Å/sec以上であることが好ましい。当該溶解速度が10Å/sec以上であると現像液に易溶で、レジストに一層向いている。また、10Å/sec以上の溶解速度を有すると、解像性が向上する場合もある。これは、上述の本実施形態の化合物及び樹脂のミクロの表面部位が溶解し、LERを低減するからと推測される。またディフェクトの低減効果がある。
前記溶解速度は、23℃にて、アモルファス膜を所定時間現像液に浸漬させ、その浸漬前後の膜厚を、目視、エリプソメーター又はQCM法等の公知の方法によって測定し決定できる。
ネガ型レジストパターンの場合、前記レジスト組成物をスピンコートして形成したアモルファス膜のKrFエキシマレーザー、極端紫外線、電子線又はX線等の放射線により露光した部分の23℃における現像液に対する溶解速度は、5Å/sec以下が好ましく、0.05~5Å/secがより好ましく、0.0005~5Å/secがさらに好ましい。当該溶解速度が5Å/sec以下であると現像液に不溶で、レジストとすることができる。また、0.0005Å/sec以上の溶解速度を有すると、解像性が向上する場合もある。これは、上述の本実施形態の化合物及び樹脂を構成成分として含む樹脂の露光前後の溶解性の変化により、現像液に溶解する未露光部と、現像液に溶解しない露光部との界面のコントラストが大きくなるからと推測される。またLERの低減、ディフェクトの低減効果がある。
本実施形態の組成物は非化学増幅型レジスト用途向けリソグラフィー用膜形成組成物(以下、感放射線性組成物とも称す)として用いることができる。前記感放射線性組成物に含有させる成分(A)(上述の本実施形態の化合物及び樹脂)は、後述するジアゾナフトキノン光活性化合物(B)と併用し、g線、h線、i線、KrFエキシマレーザー、ArFエキシマレーザー、極端紫外線、電子線又はX線を照射することにより、現像液に易溶な化合物となるポジ型レジスト用基材として有用である。g線、h線、i線、KrFエキシマレーザー、ArFエキシマレーザー、極端紫外線、電子線又はX線により、成分(A)の性質は大きくは変化しないが、現像液に難溶なジアゾナフトキノン光活性化合物(B)が易溶な化合物に変化することで、現像工程によってレジストパターンを作り得る。
前記感放射線性組成物に含有させるジアゾナフトキノン光活性化合物(B)は、ポリマー性及び非ポリマー性ジアゾナフトキノン光活性化合物を含む、ジアゾナフトキノン物質であり、一般にポジ型レジスト組成物において、感光性成分(感光剤)として用いられているものであれば特に制限なく、1種又は2種以上任意に選択して用いることができる。
また、ナフトキノンジアジドスルホン酸クロライドやベンゾキノンジアジドスルホン酸クロライドなどの酸クロライドとしては、例えば、1,2-ナフトキノンジアジド-5-スルフォニルクロライド、1、2-ナフトキノンジアジド-4-スルフォニルクロライドなどが好ましいものとして挙げられる。
前記感放射線性組成物は、スピンコートによりアモルファス膜を形成することができる。また、一般的な半導体製造プロセスに適用することができる。用いる現像液の種類によって、ポジ型レジストパターン及びネガ型レジストパターンのいずれかを作り分けることができる。
ポジ型レジストパターンの場合、前記感放射線性組成物をスピンコートして形成したアモルファス膜の23℃における現像液に対する溶解速度は、5Å/sec以下が好ましく、0.05~5Å/secがより好ましく、0.0005~5Å/secがさらに好ましい。当該溶解速度が5Å/sec以下であると現像液に不溶で、レジストとすることができる。また、0.0005Å/sec以上の溶解速度を有すると、解像性が向上する場合もある。これは、上述の本実施形態の化合物及び樹脂を構成成分として含む樹脂の露光前後の溶解性の変化により、現像液に溶解する露光部と、現像液に溶解しない未露光部との界面のコントラストが大きくなるからと推測される。またLERの低減、ディフェクトの低減効果がある。
ネガ型レジストパターンの場合、前記感放射線性組成物をスピンコートして形成したアモルファス膜の23℃における現像液に対する溶解速度は、10Å/sec以上であることが好ましい。当該溶解速度が10Å/sec以上であると現像液に易溶で、レジストに一層向いている。また、10Å/sec以上の溶解速度を有すると、解像性が向上する場合もある。これは、上述の本実施形態の化合物及び樹脂を構成成分として含む樹脂のミクロの表面部位が溶解し、LERを低減するからと推測される。またディフェクトの低減効果がある。
前記溶解速度は、23℃にて、アモルファス膜を所定時間現像液に浸漬させ、その浸漬前後の膜厚を、目視、エリプソメーター又はQCM法等の公知の方法によって測定し決定できる。
ネガ型レジストパターンの場合、前記感放射線性組成物をスピンコートして形成したアモルファス膜のKrFエキシマレーザー、極端紫外線、電子線又はX線等の放射線により照射した後、又は、20~500℃で加熱した後の露光した部分の、23℃における現像液に対する溶解速度は、5Å/sec以下が好ましく、0.05~5Å/secがより好ましく、0.0005~5Å/secがさらに好ましい。当該溶解速度が5Å/sec以下であると現像液に不溶で、レジストとすることができる。また、0.0005Å/sec以上の溶解速度を有すると、解像性が向上する場合もある。これは、上述の本実施形態の化合物及び樹脂の露光前後の溶解性の変化により、現像液に溶解する未露光部と、現像液に溶解しない露光部との界面のコントラストが大きくなるからと推測される。またLERの低減、ディフェクトの低減効果がある。
前記感放射線性組成物において、成分(A)の含有量は、固形成分全重量(成分(A)、ジアゾナフトキノン光活性化合物(B)及びその他の成分(D)などの任意に使用される固形成分の総和、以下同様。)に対して、好ましくは1~99質量%であり、より好ましくは5~95質量%、さらに好ましくは10~90質量%、特に好ましくは25~75質量%である。前記感放射線性組成物は、成分(A)の含有量が前記範囲内であると、高感度でラフネスの小さなパターンを得ることができる。
前記感放射線性組成物には、本発明の目的を阻害しない範囲で、必要に応じて、成分(A)及びジアゾナフトキノン光活性化合物(B)以外の成分として、酸発生剤、架橋剤、酸拡散制御剤、溶解促進剤、溶解制御剤、増感剤、界面活性剤、有機カルボン酸又はリンのオキソ酸若しくはその誘導体、熱及び/又は光硬化触媒、重合禁止剤、難燃剤、充填剤、カップリング剤、熱硬化性樹脂、光硬化性樹脂、染料、顔料、増粘剤、滑剤、消泡剤、レベリング剤、紫外線吸収剤、界面活性剤、着色剤、ノニオン系界面活性剤等の各種添加剤を1種又は2種以上添加することができる。なお、本明細書において、その他の成分(D)を任意成分(D)ということがある。
好ましくは1~99/99~1/0~98、
より好ましくは5~95/95~5/0~49、
さらに好ましくは10~90/90~10/0~10、
特に好ましくは20~80/80~20/0~5、
最も好ましくは25~75/75~25/0、である。
各成分の配合割合は、その総和が100質量%になるように各範囲から選ばれる。前記感放射線性組成物は、各成分の配合割合を前記範囲にすると、ラフネスに加え、感度、解像度等の性能に優れる。
本実施形態によるレジストパターンの形成方法は、上述した本実施形態の組成物(前記レジスト組成物又は感放射線性組成物)を用いてフォトレジスト層を形成した後、前記フォトレジスト層の所定の領域に放射線を照射し、現像を行う工程を含む。具体的には、本実施形態によるレジストパターンの形成方法は、基板上にレジスト膜を形成する工程と、形成されたレジスト膜を露光する工程と、前記レジスト膜を現像してレジストパターンを形成する工程とを備える。本実施形態におけるレジストパターンは多層プロセスにおける上層レジストとして形成することもできる。
界面活性剤としては特に限定されないが、例えば、イオン性や非イオン性のフッ素系及び/又はシリコン系界面活性剤等を用いることができる。これらのフッ素及び/又はシリコン系界面活性剤として、例えば、特開昭62-36663号公報、特開昭61-226746号公報、特開昭61-226745号公報、特開昭62-170950号公報、特開昭63-34540号公報、特開平7-230165号公報、特開平8-62834号公報、特開平9-54432号公報、特開平9-5988号公報、米国特許第5405720号明細書、同5360692号明細書、同5529881号明細書、同5296330号明細書、同5436098号明細書、同5576143号明細書、同5294511号明細書、同5824451号明細書記載の界面活性剤を挙げることができ、好ましくは、非イオン性の界面活性剤である。非イオン性の界面活性剤としては特に限定されないが、フッ素系界面活性剤又はシリコン系界面活性剤を用いることがさらに好ましい。
本実施形態の組成物は、下層膜用途向けリソグラフィー用膜形成組成物(以下、下層膜形成材料とも称す。)として用いることもできる。下層膜形成材料は、上述の本実施形態の化合物及び樹脂からなる群より選ばれる少なくとも1種の物質を含有する。本実施形態において前記物質は塗布性及び品質安定性の点から、下層膜形成材料中、1~100質量%であることが好ましく、10~100質量%であることがより好ましく、50~100質量%であることがさらに好ましく、100質量%であることが特に好ましい。
前記下層膜形成材料は、溶媒を含有してもよい。前記下層膜形成材料に用いられる溶媒としては、上述した物質が少なくとも溶解するものであれば、公知のものを適宜用いることができる。
前記下層膜形成材料は、インターミキシングを抑制する等の観点から、必要に応じて架橋剤を含有していてもよい。本実施形態で使用可能な架橋剤は特に限定されないが、例えば、国際公開第2013/024779号に記載の架橋剤を用いることができる。
本実施形態の下層膜形成材料には、必要に応じて架橋、硬化反応を促進させるための架橋促進剤を用いることができる。
本実施形態の下層膜形成材料には、必要に応じてラジカル重合開始剤を配合することができる。ラジカル重合開始剤としては、光によりラジカル重合を開始させる光重合開始剤であってもよいし、熱によりラジカル重合を開始させる熱重合開始剤であってもよい。ラジカル重合開始剤としては、例えば、ケトン系光重合開始剤、有機過酸化物系重合開始剤及びアゾ系重合開始剤からなる群より選ばれる少なくとも1種とすることができる。
前記下層膜形成材料は、熱による架橋反応をさらに促進させるなどの観点から、必要に応じて酸発生剤を含有していてもよい。酸発生剤としては、熱分解によって酸を発生するもの、光照射によって酸を発生するものなどが知られているが、いずれのものも使用することができる。例えば、国際公開第2013/024779号に記載のものを用いることができる。
さらに、前記下層膜形成材料は、保存安定性を向上させる等の観点から、塩基性化合物を含有していてもよい。
また、本実施形態における下層膜形成材料は、熱や光による硬化性の付与や吸光度をコントロールする目的で、他の樹脂及び/又は化合物を含有していてもよい。このような他の樹脂及び/又は化合物としては、ナフトール樹脂、キシレン樹脂ナフトール変性樹脂、ナフタレン樹脂のフェノール変性樹脂、ポリヒドロキシスチレン、ジシクロペンタジエン樹脂、(メタ)アクリレート、ジメタクリレート、トリメタクリレート、テトラメタクリレート、ビニルナフタレン、ポリアセナフチレンなどのナフタレン環、フェナントレンキノン、フルオレンなどのビフェニル環、チオフェン、インデンなどのヘテロ原子を有する複素環を含む樹脂や芳香族環を含まない樹脂;ロジン系樹脂、シクロデキストリン、アダマンタン(ポリ)オール、トリシクロデカン(ポリ)オール及びそれらの誘導体等の脂環構造を含む樹脂又は化合物等が挙げられるが、これらに特に限定されない。さらに、本実施形態における下層膜形成材料は、公知の添加剤を含有していてもよい。前記公知の添加剤としては、以下に限定されないが、例えば、熱及び/又は光硬化触媒、重合禁止剤、難燃剤、充填剤、カップリング剤、熱硬化性樹脂、光硬化性樹脂、染料、顔料、増粘剤、滑剤、消泡剤、レベリング剤、紫外線吸収剤、界面活性剤、着色剤、ノニオン系界面活性剤等が挙げられる。
前記下層膜形成材料を用いて、リソグラフィー用下層膜を形成することができる。
なお、前記組成物を用いてレジスト永久膜を作製することもできる、前記組成物を塗布してなるレジスト永久膜は、必要に応じてレジストパターンを形成した後、最終製品にも残存する永久膜として好適である。永久膜の具体例としては、半導体デバイス関係では、ソルダーレジスト、パッケージ材、アンダーフィル材、回路素子等のパッケージ接着層や集積回路素子と回路基板の接着層、薄型ディスプレー関連では、薄膜トランジスタ保護膜、液晶カラーフィルター保護膜、ブラックマトリクス、スペーサーなどが挙げられる。特に、前記組成物からなる永久膜は、耐熱性や耐湿性に優れている上に昇華成分による汚染性が少ないという非常に優れた利点も有する。特に表示材料において、重要な汚染による画質劣化の少ない高感度、高耐熱、吸湿信頼性を兼ね備えた材料となる。
下記装置を用いて有機元素分析により炭素濃度及び酸素濃度(質量%)を測定した。
装置:CHNコーダーMT-6(ヤナコ分析工業(株)製)
化合物の分子量は、Water社製Acquity UPLC/MALDI-Synapt HDMSを用いて、LC-MS分析により測定した。
また、以下の条件でゲル浸透クロマトグラフィー(GPC)分析を行い、ポリスチレン換算の重量平均分子量(Mw)、数平均分子量(Mn)、及び分散度(Mw/Mn)を求めた。
装置:Shodex GPC-101型(昭和電工(株)製)
カラム:KF-80M×3
溶離液:THF 1mL/min
温度:40℃
23℃にて、化合物をプロピレングリコールモノメチルエーテル(PGME)、シクロヘキサノン(CHN)、乳酸エチル(EL)、メチルアミルケトン(MAK)又はテトラメチルウレア(TMU)に対して3質量%溶液になるよう攪拌して溶解させた後、1週間経過させた。以下の基準に従って化合物の溶解性を評価した。
評価A:目視にていずれかの溶媒で析出物が生成していないことを確認した。
評価C:目視にていずれかの溶媒で析出物が生成されていることを確認した。
化合物の構造は、Bruker社製「Advance600II spectrometer」を用いて、以下の条件で、1H-NMR測定を行い、確認した。
周波数:400MHz
溶媒:d6-DMSO
内部標準:TMS
測定温度:23℃
攪拌機、冷却管及びビュレットを備えた内容積300mLの容器において、2-ナフトール(シグマ-アルドリッチ社製試薬)10g(69.0mmol)を120℃で溶融後、硫酸0.27gを仕込み、4-アセチルビフェニル(シグマ-アルドリッチ社製試薬)2.7g(13.8mmol)を加えて、内容物を120℃で6時間撹拌して反応を行って反応液を得た。次に反応液にN-メチル-2-ピロリドン(関東化学株式会社製)100mL、純水50mLを加えたあと、酢酸エチルにより抽出した。次に純水を加えて中性になるまで分液後、濃縮を行って溶液を得た。
得られた溶液を、カラムクロマトによる分離後、下記式(BiN-1)で表される目的化合物(BiN-1)が1.0g得られた。
得られた化合物(BiN-1)について、上述の方法により分子量を測定した結果、466であった。
得られた化合物(BiN-1)について、上述の測定条件で、NMR測定を行ったところ、以下のピークが見出され、下記式(BiN-1)の化学構造を有することを確認した。
δ(ppm)9.69(2H,O-H)、7.01~7.67(21H,Ph-H)、2.28(3H,C-H)
2-ナフトールの代わりに、o-フェニルフェノールを使用する以外は合成例1と同様に反応させ、下記式(BiP-1)で表される目的化合物が1.0g得られた。
得られた化合物(BiP-1)について、上述の方法により分子量を測定した結果、466であった。
得られた化合物(BiP-1)について、上述の測定条件で、NMR測定を行ったところ、以下のピークが見出され、下記式(BiP-1)の化学構造を有することを確認した。
δ(ppm)9.67(2H,O-H)、6.98~7.60(25H,Ph-H)、2.25(3H,C-H)
2-ナフトール(原料1)及び4-アセチルビフェニル(原料2)を下記表1のように変更し、その他は合成例1と同様に行い、各目的物を得た。
それぞれ、1H-NMRで同定した結果を表2に示す。
2-ナフトール(原料1)及び4-アセチルビフェニル(原料2)を下記表3のように変更し、水1.5mL、ドデシルメルカプタン73mg(0.35mmol)、37%塩酸2.3g(22mmol)を加え、反応温度を55℃に変更し、その他は合成例1と同様に行い、下記表4に記載の各目的物を得た。
それぞれ、1H-NMRで同定した。
ジムロート冷却管、温度計及び攪拌翼を備えた、底抜きが可能な内容積1Lの四つ口フラスコを準備した。この四つ口フラスコに、窒素気流中、合成例2で得られた化合物(BiP-1)を36.6g(70mmol、三菱ガス化学(株)製)、40質量%ホルマリン水溶液21.0g(ホルムアルデヒドとして280mmol、三菱ガス化学(株)製)及び98質量%硫酸(関東化学(株)製)0.97mLを仕込み、常圧下、100℃で還流させながら7時間反応させた。その後、希釈溶媒としてオルソキシレン(和光純薬工業(株)製試薬特級)180.0gを反応液に加え、静置後、下相の水相を除去した。さらに、中和及び水洗を行い、オルソキシレンを減圧下で留去することにより、褐色固体の樹脂(R1-BiP-1)34.1gを得た。
ジムロート冷却管、温度計及び攪拌翼を備えた、底抜きが可能な内容積1Lの四つ口フラスコを準備した。この四つ口フラスコに、窒素気流中、合成例2で得られた化合物(BiP-1)を36.6g(70mmol、三菱ガス化学(株)製)、4-ビフェニルアルデヒド50.9g(280mmol、三菱ガス化学(株)製)、アニソール(関東化学(株)製)100mL及びシュウ酸二水和物(関東化学(株)製)10mLを仕込み、常圧下、100℃で還流させながら7時間反応させた。その後、希釈溶媒としてオルソキシレン(和光純薬工業(株)製試薬特級)180.0gを反応液に加え、静置後、下相の水相を除去した。さらに、中和及び水洗を行い、有機相の溶媒および未反応の4-ビフェニルアルデヒドを減圧下で留去することにより、褐色固体の樹脂(R2-BiP-2)34.7gを得た。
攪拌機、冷却管及びビュレットを備えた内容積100mlの容器に上述の式(BiN-1)で表される化合物9.8g(21mmol)と炭酸カリウム6.2g(45mmol)とを100mlジメチルホルムアミドに加えた液を仕込み、さらに酢酸-2-クロロエチル5.5g(45mmol)を加えて、得られた反応液を90℃で12時間撹拌して反応を行なった。次に反応液から固形分をろ過で除去し、氷浴で冷却し、結晶を析出させ、ろ過を行なって分離した。
続いて攪拌機、冷却管及びビュレットを備えた内容積200mlの容器に前記結晶10g、メタノール10g、THF100g及び24%水酸化ナトリウム水溶液を仕込み、反応液を還流下で4時間撹拌して反応を行った。その後、氷浴で冷却し、反応液を濃縮し析出した固形物を濾過し、乾燥させた後、カラムクロマトによる分離精製を行い、下記式(E-BiN-1)で表される目的化合物が4.0g得られた。
400MHz-1H-NMRにより、下記式(E-BiN-1)の化学構造を有することを確認した。
1H-NMR:(d-DMSO、内部標準TMS)
δ(ppm)8.62(2H,O-H)、7.01~7.67(21H,Ph-H)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH)、2.28(3H,C-H)
熱分解温度は375℃、ガラス転移点は80℃であり、高耐熱性が確認できた。
攪拌機、冷却管及びビュレットを備えた内容積100mlの容器に前記式(BiN-1)で表される化合物9.8g(21mmol)と炭酸カリウム6.2g(45mmol)とを100mlジメチルホルムアミドに加えた液を仕込み、さらにエピクロルヒドリン4.1g(45mmol)を加えて、得られた反応液を90℃で6.5時間撹拌して反応を行なった。次に反応液から固形分をろ過で除去し、氷浴で冷却し、結晶を析出させ、濾過し、乾燥させた後、カラムクロマトによる分離精製を行い、下記式(G-BiN-1)で表される目的化合物が4.0g得られた。
得られた化合物(G-BiN-1)について、上述の測定条件で、NMR測定を行ったところ、以下のピークが見出され、下記式(G-BiN-1)の化学構造を有することを確認した。
1H-NMR:(d-DMSO、内部標準TMS)
δ(ppm)7.0~7.7(21H,Ph-H)、4.4~4.5(4H,Ph-O-CH2-CH(CH2))、3.3(2H,O-CH(CH2)-CH2-、2.6~2.8(4H,CH-CH2-O)、2.3(3H,C-H)
熱分解温度は380℃、ガラス転移点は90℃であり、高耐熱性が確認できた。
前記式(BiN-1)で表される化合物の代わりに、前記式(E-BiN-1)で表される化合物を用いた以外、合成実施例1-2と同様に反応させ、下記式(GE-BiN-1)で表される目的化合物が3.0g得られた。
400MHz-1H-NMRにより、下記式(GE-BiN-1)の化学構造を有することを確認した。
1H-NMR:(d-DMSO、内部標準TMS)
δ(ppm)7.0~7.7(21H,Ph-H)、4.4~4.5(4H,Ph-O-CH2-CH(CH2))、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH)、2.3(3H,C-H)3.3(2H,O-CH(CH2)-CH2-、2.6~2.8(4H,CH-CH2-O)
熱分解温度は375℃、ガラス転移点は85℃であり、高耐熱性が確認できた。
前記式(BiN-1)で表される化合物の代わりに、前記式(BiP-1)で表される化合物を用いた以外、合成実施例1-1と同様に反応させ、下記式(E-BiP-1)で表される目的化合物が3.3g得られた。
400MHz-1H-NMRにより、下記式(E-BiP-1)の化学構造を有することを確認した。
1H-NMR:(d-DMSO、内部標準TMS)
δ(ppm)8.62(2H,O-H)、6.98~7.60(25H,Ph-H)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH)、2.25(3H,C-H)
熱分解温度は385℃、ガラス転移点は70℃であり、高耐熱性が確認できた。
前記式(BiN-1)で表される化合物の代わりに、前記式(BiP-1)で表される化合物を用いた以外、合成実施例1-2と同様に反応させ、下記式(G-BiP-1)で表される目的化合物が3.0g得られた。
400MHz-1H-NMRにより、下記式(G-BiP-1)の化学構造を有することを確認した。
1H-NMR:(d-DMSO、内部標準TMS)
δ(ppm)7.0~7.6(25H,Ph-H)、4.4~4.5(4H,Ph-O-CH2-CH(CH2))、3.3(2H,O-CH(CH2)-CH2-、2.6~2.8(4H,CH-CH2-O)、2.3(3H,C-H)
熱分解温度は385℃、ガラス転移点は90℃であり、高耐熱性が確認できた。
前記式(E-BiN-1)で表される化合物の代わりに、前記式(E-BiP-1)で表される化合物を用いた以外、合成実施例2-2と同様に反応させ、下記式(GE-BiP-1)で表される目的化合物が3.3g得られた。
400MHz-1H-NMRにより、下記式(GE-BiP-1)の化学構造を有することを確認した。
1H-NMR:(d-DMSO、内部標準TMS)
δ(ppm)7.0~7.6(25H,Ph-H)、4.4~4.5(4H,Ph-O-CH2-CH(CH2))、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH)、3.3(2H,O-CH(CH2)-CH2-、2.6~2.8(4H,CH-CH2-O)、2.3(3H,C-H)
合成実施例1-1の原料である前記式(BiN-1)で表される化合物を下記表5のように変更し、その他は合成実施例1-1と同様の条件にて合成を行い、それぞれ、目的物を得た。各化合物の構造は400MHz-1H-NMR(d-DMSO、内部標準TMS)およびLC-MSで分子量を確認することにより、同定した。
合成実施例1-2の原料である前記式(BiN-1)で表される化合物を下記表5のように変更し、その他は合成実施例1-2と同様の条件にて合成を行い、それぞれ、目的物を得た。各化合物の構造は400MHz-1H-NMR(d-DMSO、内部標準TMS)およびLC-MSで分子量を確認することにより、同定した。
合成実施例1-3の原料である前記式(E-BiN-1)で表される化合物を下記表5のように変更し、その他は合成実施例1-3と同様の条件にて合成を行い、それぞれ、目的物を得た。各化合物の構造は400MHz-1H-NMR(d-DMSO、内部標準TMS)およびLC-MSで分子量を確認することにより、同定した。
攪拌機、冷却管及びビュレットを備えた内容積500mlの容器に上述の式(R1-BiP-1)で表される樹脂29.8gと炭酸カリウム6.2g(45mmol)とを200mlジメチルホルムアミドに加えた液を仕込み、さらに酢酸-2-クロロエチル5.5g(45mmol)を加えて、得られた反応液を90℃で12時間撹拌して反応を行なった。次に反応液から固形分をろ過で除去し、氷浴で冷却し、固体を析出させ、ろ過を行なって分離した。
続いて攪拌機、冷却管及びビュレットを備えた内容積200mlの容器に前記固体20g、メタノール10g、THF100g及び24%水酸化ナトリウム水溶液を仕込み、反応液を還流下で4時間撹拌して反応を行った。その後、氷浴で冷却し、反応液を濃縮し析出した固形物を濾過し、乾燥させることにより、褐色固体の樹脂(E-R1-BiP-1)24.5gを得た。
攪拌機、冷却管及びビュレットを備えた内容積500mlの容器に前記式(R1-BiP-1)で表される樹脂29.8gと炭酸カリウム6.2g(45mmol)とを200mlジメチルホルムアミドに加えた液を仕込み、さらにエピクロルヒドリン4.1g(45mmol)を加えて、得られた反応液を90℃で6.5時間撹拌して反応を行なった。次に反応液から固形分をろ過で除去し、氷浴で冷却し、固体を析出させ、濾過し、乾燥させることにより、褐色固体の樹脂(G-R1-BiP-1)25.6gを得た。
前記式(R1-BiP-1)で表される樹脂の代わりに、前記式(E-R1-BiP-1)で表される樹脂を29.8g用いた以外、合成実施例16-2と同様に反応させ、褐色固体の下記式GE-R1-BiP-1で表される樹脂が22.4g得られた。
攪拌機、冷却管及びビュレットを備えた内容積500mlの容器に上述の式(R2-BiP-1)で表される樹脂29.8gと炭酸カリウム6.2g(45mmol)とを200mlジメチルホルムアミドに加えた液を仕込み、さらに酢酸-2-クロロエチル5.5g(45mmol)を加えて、得られた反応液を90℃で12時間撹拌して反応を行なった。次に反応液から固形分をろ過で除去し、氷浴で冷却し、固体を析出させ、ろ過を行なって分離した。
続いて攪拌機、冷却管及びビュレットを備えた内容積200mlの容器に前記固体20g、メタノール10g、THF100g及び24%水酸化ナトリウム水溶液を仕込み、反応液を還流下で4時間撹拌して反応を行った。その後、氷浴で冷却し、反応液を濃縮し析出した固形物を濾過し、乾燥させることにより、褐色固体の樹脂(E-R2-BiP-1)27.5gを得た。
攪拌機、冷却管及びビュレットを備えた内容積500mlの容器に前記式(R2-BiP-1)で表される樹脂29.8gと炭酸カリウム6.2g(45mmol)とを200mlジメチルホルムアミドに加えた液を仕込み、さらにエピクロルヒドリン4.1g(45mmol)を加えて、得られた反応液を90℃で7.0時間撹拌して反応を行なった。次に反応液から固形分をろ過で除去し、氷浴で冷却し、固体を析出させ、濾過し、乾燥させることにより、褐色固体の樹脂(G-R2-BiP-1)25.6gを得た。
前記式(R1-BiP-1)で表される樹脂の代わりに、前記式(E-R1-BiP-1)で表される樹脂を29.8g用いた以外、合成実施例16-2と同様に反応させ、褐色固体の下記式GE-R1-BiP-1で表される樹脂が22.4g得られた。
ジムロート冷却管、温度計及び攪拌翼を備えた、底抜きが可能な内容積10Lの四つ口フラスコを準備した。この四つ口フラスコに、窒素気流中、1,5-ジメチルナフタレン1.09kg(7mol、三菱ガス化学(株)製)、40質量%ホルマリン水溶液2.1kg(ホルムアルデヒドとして28mol、三菱ガス化学(株)製)及び98質量%硫酸(関東化学(株)製)0.97mLを仕込み、常圧下、100℃で還流させながら7時間反応させた。その後、希釈溶媒としてエチルベンゼン(和光純薬工業(株)製試薬特級)1.8kgを反応液に加え、静置後、下相の水相を除去した。さらに、中和及び水洗を行い、エチルベンゼン及び未反応の1,5-ジメチルナフタレンを減圧下で留去することにより、淡褐色固体のジメチルナフタレンホルムアルデヒド樹脂1.25kgを得た。
得られたジメチルナフタレンホルムアルデヒドの分子量は、Mn:562、であった。
得られた樹脂(CR-1)は、Mn:885、Mw:2220、Mw/Mn:4.17であった。
前記合成実施例1-1~17-3の化合物および樹脂、合成比較例1の樹脂CR-1につき、溶解性の評価を行った。結果を下記表6に示す。
・架橋剤:三和ケミカル社製 ニカラックMX270(ニカラック)
有機溶媒:プロピレングリコールモノメチルエーテルアセテートアセテート(PGMEA)
・ノボラック:群栄化学社製 PSM4357
・架橋剤:
三菱ガス化学製 ジアリルビスフェノールA型シアネート(DABPA-CN)
小西化学工業製 ジアリルビスフェノールA(BPA-CA)
小西化学工業製 ベンゾオキサジン(BF-BXZ)
日本化薬製 ビフェニルアラルキル型エポキシ樹脂(NC-3000-L)
・有機溶媒:
プロピレングリコールモノメチルエーテルアセテートアセテート(PGMEA)
以下に示す条件でエッチング試験を行い、エッチング耐性を評価した。評価結果を表6に示す。
エッチング装置:サムコインターナショナル社製「RIE-10NR」
出力:50W
圧力:20Pa
時間:2min
エッチングガス
Arガス流量:CF4ガス流量:O2ガス流量=50:5:5(sccm)
まず、実施例1-1において用いる化合物(E-BiN-1)に代えてノボラック(群栄化学社製「PSM4357」)を用いること以外は、実施例1-1と同様の条件で、ノボラックの下層膜を作製した。そして、このノボラックの下層膜を対象として、上述のエッチング試験を行い、そのときのエッチングレートを測定した。
そして、ノボラックの下層膜のエッチングレートを基準として、以下の評価基準でエッチング耐性を評価した。
A:ノボラックの下層膜に比べてエッチングレートが、-10%未満
B:ノボラックの下層膜に比べてエッチングレートが、-10%~+5%
C:ノボラックの下層膜に比べてエッチングレートが、+5%超
また、上述のように実施例の化合物は耐熱性に優れていた。
次に、E-BiN-1、E-BiP-1、G-BiN-1、G-BiP-1、GE-BiN-1、GE-BiP-1を含むリソグラフィー用下層膜形成材料の各溶液を膜厚300nmのSiO2基板上に塗布して、240℃で60秒間、さらに400℃で120秒間ベークすることにより、膜厚70nmの下層膜を形成した。この下層膜上に、ArF用レジスト溶液を塗布し、130℃で60秒間ベークすることにより、膜厚140nmのフォトレジスト層を形成した。なお、ArFレジスト溶液としては、下記式(11)の化合物:5質量部、トリフェニルスルホニウムノナフルオロメタンスルホナート:1質量部、トリブチルアミン:2質量部、及びPGMEA:92質量部を配合して調製したものを用いた。
下層膜の形成を行わないこと以外は、実施例48と同様にして、フォトレジスト層をSiO2基板上に直接形成し、ポジ型のレジストパターンを得た。結果を表8に示す。
現像後のレジストパターン形状の相違から、実施例48~53において用いたリソグラフィー用下層膜形成材料は、レジスト材料との密着性がよいことが示された。
実施例1-1~2-3のリソグラフィー用下層膜形成材料の溶液を膜厚300nmのSiO2基板上に塗布して、240℃で60秒間、さらに400℃で120秒間ベークすることにより、膜厚80nmの下層膜を形成した。この下層膜上に、珪素含有中間層材料を塗布し、200℃で60秒間ベークすることにより、膜厚35nmの中間層膜を形成した。さらに、この中間層膜上に、前記ArF用レジスト溶液を塗布し、130℃で60秒間ベークすることにより、膜厚150nmのフォトレジスト層を形成した。なお、珪素含有中間層材料としては、特開2007-226170号公報<合成例1>に記載の珪素原子含有ポリマーを用いた。
その後、サムコインターナショナル社製 RIE-10NRを用いて、得られたレジストパターンをマスクにして珪素含有中間層膜(SOG)のドライエッチング加工を行い、続いて、得られた珪素含有中間層膜パターンをマスクにした下層膜のドライエッチング加工と、得られた下層膜パターンをマスクにしたSiO2膜のドライエッチング加工とを順次行った。
(レジストパターンのレジスト中間層膜へのエッチング条件)
出力:50W
圧力:20Pa
時間:1min
エッチングガス
Arガス流量:CF4ガス流量:O2ガス流量=50:8:2(sccm)
出力:50W
圧力:20Pa
時間:2min
エッチングガス
Arガス流量:CF4ガス流量:O2ガス流量=50:5:5(sccm)
出力:50W
圧力:20Pa
時間:2min
エッチングガス
Arガス流量:C5F12ガス流量:C2F6ガス流量:O2ガス流量=50:4:3:1(sccm)
上述のようにして得られたパターン断面(エッチング後のSiO2膜の形状)を、(株)日立製作所製電子顕微鏡(S-4800)を用いて観察したところ、本実施形態の下層膜を用いた実施例は、多層レジスト加工におけるエッチング後のSiO2膜の形状は矩形であり、欠陥も認められず良好であることが確認された。
前記合成例、及び合成実施例で合成した各化合物を用いて、下記表9に示す配合で光学部品形成組成物を調製した。なお、表9中の光学部品形成組成物の各成分のうち、酸発生剤、架橋剤、酸拡散抑制剤、及び溶媒については、以下のものを用いた。
・酸発生剤:みどり化学社製 ジターシャリーブチルジフェニルヨードニウムノナフルオロメタンスルホナート(DTDPI)
・架橋剤:三和ケミカル社製 ニカラックMX270(ニカラック)
有機溶媒:プロピレングリコールモノメチルエーテルアセテートアセテート(PGMEA)
均一状態の光学部品形成組成物を清浄なシリコンウェハー上に回転塗布した後、110℃のオーブン中でプレベーク(prebake:PB)して、厚さ1μmの光学部品形成膜を形成した。調製した光学部品形成組成物について、膜形成が良好な場合には「A」、形成した膜に欠陥がある場合には「C」と評価した。
前記合成例、及び合成実施例で合成した各化合物を用いて、下記表10に示す配合でレジスト組成物を調製した。なお、表10中の光学部品形成組成物の各成分のうち、酸発生剤、架橋剤、酸拡散抑制剤、及び溶媒については、以下のものを用いた。
・酸発生剤:みどり化学社製 トリフェニルホスホニウム トリフルオロメタンスルホネート
・架橋剤:三和ケミカル社製 ニカラックMX270
・酸拡散抑制剤:東京化成工業社製 トリオクチルアミン
・有機溶媒:東京化成工業社製 プロピレングリコールモノメチルエーテル(PGME)
(1)レジスト組成物の保存安定性及び薄膜形成
レジスト組成物の保存安定性は、レジスト組成物を作成後、23℃、50%RHにて3日間静置し、析出の有無を目視にて観察することにより評価した。3日間静置後のレジスト組成物において、均一溶液であり析出がない場合にはA、析出がある場合はCと評価した。また、均一状態のレジスト組成物を清浄なシリコンウェハー上に回転塗布した後、110℃のオーブン中で露光前ベーク(PB)して、厚さ40nmのレジスト膜を形成した。作成したレジスト組成物について、薄膜形成が良好な場合にはA、形成した膜に欠陥がある場合にはCと評価した。
均一なレジスト組成物を清浄なシリコンウェハー上に回転塗布した後、110℃のオーブン中で露光前ベーク(PB)して、厚さ60nmのレジスト膜を形成した。得られたレジスト膜に対して、電子線描画装置(ELS-7500、(株)エリオニクス社製)を用いて、50nm、40nm及び30nm間隔の1:1のラインアンドスペース設定の電子線を照射した。当該照射後に、レジスト膜を、それぞれ所定の温度で、90秒間加熱し、PGMEに60秒間浸漬して現像を行った。その後、レジスト膜を、超純水で30秒間洗浄、乾燥して、ネガ型のレジストパターンを形成した。形成されたレジストパターンについて、ラインアンドスペースを走査型電子顕微鏡((株)日立ハイテクノロジー製S-4800)により観察し、レジスト組成物の電子線照射による反応性を評価した。
感度は、パターンを得るために必要な単位面積当たりの最小のエネルギー量で示し、以下に従って評価した。
A:50μC/cm2未満でパターンが得られた場合
C:50μC/cm2以上でパターンが得られた場合
パターン形成は、得られたパターン形状をSEM(走査型電子顕微鏡:Scanning Electron Microscope)にて観察し、以下に従って評価した。
A:矩形なパターンが得られた場合
B:ほぼ矩形なパターンが得られた場合
C:矩形でないパターンが得られた場合
また、湿式プロセスが適用可能であり、耐熱性及びエッチング耐性に優れるフォトレジスト下層膜を形成するために有用な化合物、樹脂及びリソグラフィー用膜形成組成物を実現することができる。そして、このリソグラフィー用膜形成組成物は、耐熱性が高く、溶媒溶解性も高い、特定構造を有する化合物又は樹脂を用いているため、高温ベーク時の膜の劣化が抑制され、酸素プラズマエッチング等に対するエッチング耐性にも優れたレジスト及び下層膜を形成することができる。さらには、下層膜を形成した場合、レジスト層との密着性にも優れるので、優れたレジストパターンを形成することができる。
さらには屈折率が高く、また低温~高温処理によって着色が抑制されることから、各種光学部品形成組成物としても有用である。
特に、本発明はリソグラフィー用レジスト、リソグラフィー用下層膜及び多層レジスト用下層膜及び光学部品の分野において、特に有効に利用可能である。
また、明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (28)
- 下記式(0)で表される、化合物。
(式(0)中、RYは、炭素数1~30のアルキル基又は炭素数6~30のアリール基であり、
RZは、炭素数1~60のN価の基又は単結合であり、
RTは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、RTの少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
Xは、酸素原子、硫黄原子又は無架橋であることを表し、
mは、各々独立して0~9の整数であり、ここで、mの少なくとも1つは1~9の整数であり、
Nは、1~4の整数であり、Nが2以上の整数の場合、N個の[ ]内の構造式は同一であっても異なっていてもよく、
rは、各々独立して0~2の整数である。) - 前記式(0)で表される化合物が下記式(1)で表される化合物である、請求項1に記載の化合物。
(式(1)中、R0は、前記RYと同義であり、
R1は、炭素数1~60のn価の基又は単結合であり、
R2~R5は、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、R2~R5の少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
m2及びm3は、各々独立して、0~8の整数であり、
m4及びm5は、各々独立して、0~9の整数であり、
但し、m2、m3、m4及びm5は同時に0となることはなく、
nは前記Nと同義であり、ここで、nが2以上の整数の場合、n個の[ ]内の構造式は同一であっても異なっていてもよく、
p2~p5は、前記rと同義である。) - 前記式(0)で表される化合物が下記式(2)で表される化合物である、請求項1に記載の化合物。
(式(2)中、R0Aは、前記RYと同義であり、
R1Aは、炭素数1~60のnA価の基又は単結合であり、
R2Aは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、R2Aの少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
nAは、前記Nと同義であり、ここで、nAが2以上の整数の場合、nA個の[ ]内の構造式は同一であっても異なっていてもよく、
XAは、前記Xと同義あり、
m2Aは、各々独立して、0~7の整数であり、但し、少なくとも1つのm2Aは1~7の整数であり、
qAは、各々独立して、0又は1である。) - 前記式(1)で表される化合物が下記式(1-1)で表される化合物である、請求項2に記載の化合物。
(式(1-1)中、R0、R1、R4、R5、n、p2~p5、m4及びm5は、前記と同義であり、
R6~R7は、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基であり、
R10~R11は、各々独立して、水素原子又はヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基であり、
ここで、R10~R11の少なくとも1つはヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基から選ばれる1つの基であり、
m6及びm7は、各々独立して、0~7の整数であり、
但し、m4、m5、m6及びm7は同時に0となることはない。) - 前記式(2)で表される化合物が下記式(2-1)で表される化合物である、請求項3に記載の化合物。
(式(2-1)中、R0A、R1A、nA、qA及びXA、は、前記式(2)で説明したものと同義である。
R3Aは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基であり、
R4Aは、各々独立して、水素原子又はヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基であり、
ここで、R4Aの少なくとも1つはヒドロキシアルキル基、グリシジルオキシアルキル基又はグリシジル基であり、
m6Aは、各々独立して、0~5の整数である。) - 請求項1に記載の化合物をモノマーとして得られる、樹脂。
- 下記式(3)で表される構造を有する、請求項7に記載の樹脂。
(式(3)中、
Lは、置換基を有していてもよい炭素数1~30のアルキレン基、置換基を有していてもよい炭素数6~30のアリーレン基、置換基を有していてもよい炭素数1~30のアルコキシレン基又は単結合であり、前記アルキレン基、前記アリーレン基、前記アルコキシレン基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、
R0は、前記RYと同義であり、
R1は、炭素数1~60のn価の基又は単結合であり、
R2~R5は、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、m2及びm3は、各々独立して、0~8の整数であり、
m4及びm5は、各々独立して、0~9の整数であり、
但し、m2、m3、m4及びm5は同時に0となることはなく、R2~R5の少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基である。
nは前記Nと同義であり、ここで、nが2以上の整数の場合、n個の[ ]内の構造式は同一であっても異なっていてもよく、
p2~p5は、前記rと同義である。) - 下記式(4)で表される構造を有する、請求項7に記載の樹脂。
(式(4)中、Lは、置換基を有していてもよい炭素数1~30のアルキレン基、置換基を有していてもよい炭素数6~30のアリーレン基、置換基を有していてもよい炭素数1~30のアルコキシレン基又は単結合であり、前記アルキレン基、前記アリーレン基、前記アルコキシレン基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、
R0Aは、前記RYと同義であり、
R1Aは、炭素数1~30のnA価の基又は単結合であり、
R2Aは、各々独立して、置換基を有していてもよい炭素数1~30のアルキル基、置換基を有していてもよい炭素数6~30のアリール基、置換基を有していてもよい炭素数2~30のアルケニル基、置換基を有していてもよい炭素数1~30のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基或いは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合又はエステル結合を含んでいてもよく、ここで、R2Aの少なくとも1つは水酸基の水素原子がヒドロキシアルキル基で置換された基又はグリシジル基で置換された基を含み、
nAは、前記Nと同義であり、ここで、nAが2以上の整数の場合、nA個の[ ]内の構造式は同一であっても異なっていてもよく、
XAは、前記Xと同義あり、
m2Aは、各々独立して、0~7の整数であり、但し、少なくとも1つのm2Aは1~6の整数であり、
qAは、各々独立して、0又は1である。) - 請求項1~6のいずれか一項に記載の化合物及び請求項7~9のいずれか一項に記載の樹脂からなる群より選ばれる1種以上を含有する、組成物。
- 溶媒をさらに含有する、請求項10に記載の組成物。
- 酸発生剤をさらに含有する、請求項10又は請求項11に記載の組成物。
- 架橋剤をさらに含有する、請求項10~12のいずれか一項に記載の組成物。
- 前記架橋剤が、フェノール化合物、エポキシ化合物、シアネート化合物、アミノ化合物、ベンゾオキサジン化合物、メラミン化合物、グアナミン化合物、グリコールウリル化合物、ウレア化合物、イソシアネート化合物及びアジド化合物からなる群より選ばれる少なくとも1種である、請求項13に記載の組成物。
- 前記架橋剤が、少なくとも1つのアリル基を有する、請求項13又は請求項14に記載の組成物。
- 前記架橋剤の含有量が、請求項1~6のいずれか一項に記載の化合物及び請求項7~9のいずれか一項に記載の樹脂からなる群より選ばれる1種以上を含有する組成物の合計質量100質量部に対し、0.1~100質量部である、請求項13~請求項15のいずれか一項に記載の組成物。
- 架橋促進剤をさらに含有する、請求項13~16のいずれか一項に記載の組成物。
- 前記架橋促進剤が、アミン類、イミダゾール類、有機ホスフィン類、及びルイス酸からなる群より選ばれる少なくとも1種である、請求項17に記載の組成物。
- 前記架橋促進剤の含有量が、請求項1~6のいずれか一項に記載の化合物及び請求項7~9のいずれか一項に記載の樹脂からなる群より選ばれる1種以上を含有する組成物の合計質量100質量部に対し、0.1~5質量部である、請求項17又は請求項18に記載の組成物。
- ラジカル重合開始剤をさらに含有する、請求項10~19のいずれか一項に記載の組成物。
- 前記ラジカル重合開始剤が、ケトン系光重合開始剤、有機過酸化物系重合開始剤及びアゾ系重合開始剤からなる群より選ばれる少なくとも1種である、請求項10~20のいずれか一項に記載の組成物。
- 前記ラジカル重合開始剤の含有量が、請求項1~6のいずれか一項に記載の化合物及び請求項7~9のいずれか一項に記載の樹脂からなる群より選ばれる1種以上を含有する組成物の合計質量100質量部に対し、0.05~25質量部である、請求項10~21のいずれか一項に記載の組成物。
- リソグラフィー用膜形成に用いられる、請求項10~22のいずれか一項に記載の組成物。
- レジスト永久膜形成に用いられる、請求項10~請求項22のいずれか一項に記載の組成物。
- 光学部品形成に用いられる、請求項10~請求項22のいずれか一項に記載の組成物。
- 基板上に、請求項23に記載の組成物を用いてフォトレジスト層を形成した後、前記フォトレジスト層の所定の領域に放射線を照射し、現像を行う工程を含む、レジストパターン形成方法。
- 基板上に、請求項23に記載の組成物を用いて下層膜を形成し、前記下層膜上に、少なくとも1層のフォトレジスト層を形成した後、前記フォトレジスト層の所定の領域に放射線を照射し、現像を行う工程を含む、レジストパターン形成方法。
- 基板上に、請求項23に記載の組成物を用いて下層膜を形成し、前記下層膜上に、レジスト中間層膜材料を用いて中間層膜を形成し、前記中間層膜上に、少なくとも1層のフォトレジスト層を形成した後、前記フォトレジスト層の所定の領域に放射線を照射し、現像してレジストパターンを形成し、その後、前記レジストパターンをマスクとして前記中間層膜をエッチングし、得られた中間層膜パターンをエッチングマスクとして前記下層膜をエッチングし、得られた下層膜パターンをエッチングマスクとして基板をエッチングすることにより基板にパターンを形成する工程を含む、回路パターン形成方法。
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KR20190033536A (ko) | 2019-03-29 |
JP7069529B2 (ja) | 2022-05-18 |
JPWO2018016615A1 (ja) | 2019-05-09 |
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