WO2018117167A1 - 感光性化合物、該感光性化合物を含有する光酸発生剤及びレジスト組成物、並びに、該レジスト組成物を用いたデバイスの製造方法 - Google Patents
感光性化合物、該感光性化合物を含有する光酸発生剤及びレジスト組成物、並びに、該レジスト組成物を用いたデバイスの製造方法 Download PDFInfo
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- WO2018117167A1 WO2018117167A1 PCT/JP2017/045771 JP2017045771W WO2018117167A1 WO 2018117167 A1 WO2018117167 A1 WO 2018117167A1 JP 2017045771 W JP2017045771 W JP 2017045771W WO 2018117167 A1 WO2018117167 A1 WO 2018117167A1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
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- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- DUSJKWJMEWTXFC-UHFFFAOYSA-N sulfanium;methyl sulfate Chemical compound [SH3+].COS([O-])(=O)=O DUSJKWJMEWTXFC-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C395/00—Compounds containing tellurium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
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- 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
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- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- 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
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- 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
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- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2059—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a scanning corpuscular radiation beam, e.g. an electron beam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Definitions
- Some embodiments of the invention relate to photosensitive compounds. More specifically, the present invention relates to a photosensitive compound containing a divalent Te atom that is suitably used for a resist composition for lithography using light having a short wavelength such as KrF, particularly an electron beam or extreme ultraviolet rays as an exposure source. Some embodiments of the present invention also relate to a photoacid generator and a resist composition containing the photosensitive compound, and a device manufacturing method using the resist composition.
- the demand for miniaturization of lithography technology has increased due to the high integration of devices, such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet rays (EUV, wavelength 13.5 nm).
- light having a short wavelength and a particle beam such as an electron beam (EB) tend to be used for exposure.
- Lithography technology using light with a short wavelength, particularly extreme ultraviolet rays (EUV) or electron beams can be manufactured by single patterning, and thus shows high sensitivity to extreme ultraviolet rays (EUV) or electron beams.
- EUV extreme ultraviolet rays
- the need for resist compositions is expected to increase further in the future.
- the resist composition is required to have high sensitivity to the exposure light source and to improve the lithographic characteristics having a resolution capable of reproducing the formation of a fine dimensional pattern.
- a resist composition that satisfies such requirements a chemically amplified resist composition using a photoacid generator is known (Patent Document 1).
- the power required to irradiate the laser from the light source is not sufficient, and the dose is increased in order to efficiently generate acid from the photoacid generator in the resist composition during exposure. Has its limits. Therefore, improvement of the acid generation efficiency of the photo-acid generator in a resist composition is calculated
- Conventional chemically amplified resist compositions are difficult to satisfy simultaneously the characteristics of sensitivity, resolution, depth of focus and pattern performance with respect to KrF excimer laser, ArF excimer laser, electron beam and extreme ultraviolet (EUV).
- a conventional chemically amplified resist composition for electron beam or EUV has low absorption of electron beam or EUV, and it is difficult to simultaneously satisfy the characteristics of sensitivity, resolution, depth of focus and pattern performance for electron beam or EUV. .
- the present inventors have included a compound having a specific metal as a photosensitive compound in the resist composition, so that light having a short wavelength such as KrF, particularly EUV or electron beam, etc.
- a short wavelength such as KrF, particularly EUV or electron beam, etc.
- one aspect of the present invention is a photosensitive compound containing a divalent Te atom. More specifically, the skeleton has any skeleton selected from an onium salt skeleton, a diazomethane skeleton, an imide skeleton, and an oxime skeleton, and the skeleton includes at least one Te atom-containing group represented by the following formula (1). It is the photosensitive compound which has.
- each R 1 is independently a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms; and an aryl group having 5 to 20 carbon atoms; Any or all of the hydrogen atoms of the hydrocarbon group and the aryl group may be substituted with a substituent, and when the hydrocarbon group has a methylene group, at least one A divalent heteroatom-containing group may be included instead of the methylene group, and the aryl group may include a heteroatom instead of at least one carbon atom in the ring structure, and * represents the skeleton and The binding site of is shown.
- Another embodiment of the present invention is a photoacid generator and a resist composition containing the photosensitive compound. Furthermore, another aspect of the present invention provides a step of forming a resist film on a substrate using the resist composition, a step of exposing the resist film, and developing the exposed resist film to form a resist pattern. A process for manufacturing a device.
- the photosensitive compound of one embodiment of the present invention contains a specific metal, so that film absorption with respect to light having a short wavelength such as KrF, particularly extreme ultraviolet (EUV) or electron beam is increased, and ionization efficiency is improved. Since secondary electron generation efficiency is high, sensitivity, resolution, and pattern performance are excellent.
- a short wavelength such as KrF, particularly extreme ultraviolet (EUV) or electron beam
- EUV extreme ultraviolet
- the photosensitive compound of one aspect of the present invention contains a divalent Te atom. Since the photosensitive compound contains a divalent Te atom, film absorption to light with a short wavelength such as KrF, particularly EUV or an electron beam is increased, and ionization efficiency is high and secondary electron generation efficiency is high. Go up. Therefore, it is considered that the resist composition containing the photosensitive compound has high sensitivity.
- Examples of the photosensitive compound include a skeleton selected from an onium salt skeleton, a diazomethane skeleton, an imide skeleton, and an oxime skeleton, and the skeleton includes a Te atom-containing group represented by the following formula (1). Things.
- each R 1 is independently a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms; and an aryl group having 5 to 20 carbon atoms; Any or all of the hydrogen atoms of the hydrocarbon group and the aryl group may be substituted with a substituent, and when the hydrocarbon group has a methylene group, at least one A divalent heteroatom-containing group may be included instead of the methylene group, and the aryl group may include a heteroatom instead of at least one carbon atom in the ring structure, and * represents the skeleton.
- the binding site is shown.
- the Te atom-containing group may be directly bonded to the skeleton, or may be bonded via a divalent linking group.
- Examples of the divalent linking group include a linear, branched or cyclic divalent hydrocarbon group; an arylene group; and a group in which these groups are bonded via an oxygen atom, a sulfur atom, or a nitrogen atom-containing group.
- Examples of the divalent hydrocarbon group include divalent hydrocarbon groups obtained by removing one hydrogen from the hydrocarbon group of R 1 .
- Examples of the arylene group include those obtained by removing one hydrogen from the aryl group of R 1 to be divalent.
- linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms examples include linear alkyl groups such as methyl, ethyl, n-propyl and n-butyl; Branched alkyl groups such as isopropyl and t-butyl; A cyclic alkyl group such as a cyclobutyl group, a cyclopentyl group and a cyclohexyl group; and an alkenyl group in which at least one carbon-carbon single bond of the alkyl group is substituted with a carbon-carbon double bond; And an alkynyl group in which at least one carbon-carbon single bond of the alkyl group is substituted with a carbon-carbon triple bond.
- spiro-type cyclic alkyl groups such as spiro [3,4] octyl group and spirobicyclopentyl group; bridges such as norbornyl group, tricyclodecanyl group, tetracyclododecanyl group and adamantyl group
- An alkyl group such as a condensed cyclic alkyl group having a decalin and a steroid skeleton;
- the skeleton may contain one divalent heteroatom-containing group selected from the group consisting of NH—CO—O—, —O—CO—NH—, —S—, —SO— and —SO 2 —. Good.
- a hydrogen atom bonded to a nitrogen atom is an alkyl group (R Sp ) or It may be substituted with an aryl group (Ar Sp ).
- R sp and Ar sp will be described later.
- the hydrocarbon group containing a hetero atom-containing group include an alkoxy group; an alkylcarbonyloxy group; a hydrocarbon group having a heterocyclic structure such as a lactone structure, a sultone structure, and a lactam structure;
- aryl group having 5 to 20 carbon atoms examples include monovalent aromatic hydrocarbon groups such as phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group and azulenyl group. Moreover, it may be a monovalent aromatic heterocyclic group containing a hetero atom instead of the carbon atom in the ring of the aromatic hydrocarbon group.
- aromatic heterocyclic group examples include monovalent aromatic heterocyclic groups having a skeleton such as furan, thiophene, pyran, chromene, thianthrene, dibenzothiophene, and xanthene.
- the hydrocarbon group and aryl group as R 1 may have a substituent.
- the substituent for R 1 include an alkyl group (R Sp ); an alkyl group containing the above divalent heteroatom-containing group in the skeleton instead of at least one methylene group of the alkyl group; carbon-carbon of the alkyl group Examples thereof include an alkenyl group in which at least one single bond is substituted with a carbon-carbon double bond; an aryl group (Ar Sp ); a hydroxy group; and a halogen atom.
- R Sp examples include linear, branched, or cyclic alkyl groups.
- Ar Sp include aromatic hydrocarbon groups having 12 or less carbon atoms such as a phenyl group and a naphthyl group, and aromatic heterocyclic groups that may contain a hetero atom in the ring structure in place of the carbon atom. It is done.
- Examples of the alkyl group (R Sp ), alkenyl group, and aryl group (Ar Sp ) as a substituent include the same alkyl groups, alkenyl groups, and aryl groups as those described above for R 1 .
- the halogen atom as the substituent for R 1 include a fluorine atom, a chlorine atom and a bromine atom.
- R 1 has a substituent
- the total number of carbon atoms of each R 1 including the substituent is preferably 1 to 20, more preferably 5 to 15, and more preferably 6 to 10. It is particularly preferred.
- an alkyl group such as a methyl group, an alkoxy group, a hydroxy group, and an aryl group are preferable.
- R 1 is preferably an alkyl group such as a methyl group and an n-butyl group, and an aryl group such as a phenyl group and a naphthyl group.
- Photosensitive compound having an onium salt skeleton When the photosensitive compound according to some embodiments of the present invention has an onium salt skeleton, examples thereof include those represented by the following formula (2). However, the present invention is not limited to this.
- Y is either selected from the group which consists of an iodine atom, a sulfur atom, a selenium atom, and a tellurium atom.
- n is 2
- Y is any of a sulfur atom, a selenium atom, and a tellurium atom
- n is 3.
- R 2 is independently selected from the same options as R 1 , and in formula (2), at least one of R 2 has the Te atom-containing group as a substituent. Examples of the substituent for R 2 include the same as the substituent for R 1 .
- Preferred examples of the substituent for R 2 include an alkyl group, an ester group, a hydroxy group, a sulfonyl group, and a fluoro group.
- R 2 has the Te atom-containing group
- preferred R 2 is preferably an aryl group having the Te atom-containing group from the viewpoint of film density and solubility, and among the aryl groups, the Te atom-containing group is preferable. And a naphthyl group having a Te atom-containing group are more preferred.
- R 2 does not have the Te atom-containing group
- R 2 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, from the viewpoint of solubility.
- alkyl groups such as n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and adamantyl group, and aryl groups.
- any two or more of R 2 may be bonded to each other to form a ring structure together with Y, and the ring structure may contain a hetero atom.
- Y + is preferably bonded to a divalent hydrocarbon group without being directly bonded to the hetero atom.
- Examples of the cation in which any two or more of R 2 are bonded to each other to form a ring structure with Y include the following.
- Y is any of a sulfur atom, a selenium atom, and a tellurium atom.
- —R 3 —Te—R 1 corresponds to R 2 having a Te atom-containing group represented by the above formula (1). .
- the cation having one Te atom-containing group is shown.
- Te atom-containing group may have two or more, and the present invention is not limited to the following examples.
- R 3 include the above linking groups.
- the photosensitive compound according to some embodiments of the present invention preferably has two or more Te atom-containing groups represented by the above formula (1) because the absorption to an electron beam or EUV is high.
- the photosensitive compound which is one embodiment of the present invention is preferably an onium salt compound represented by the following formula (3) or (4), wherein Y is an iodine atom and a sulfur atom.
- the cation of the onium salt compound represented by the above formula (3) or (4) represents a monocation, but may be a polycation, and the anion when it is a polycation corresponds to it.
- R 1 , R 2 , R 3 and X in the above formulas (3) and (4) are selected from the same options as R 1 , R 2 , R 3 and X ⁇ in the above formulas (1) and (2). . X - will be described in detail later.
- —R 3 —Te—R 1 corresponds to R 2 having a Te atom-containing group represented by the above formula (1) as described above.
- R 2 in the above formulas (3) and (4) may further have some Te atom-containing groups.
- Specific examples of the structure when R 3 of the onium salt compound represented by the above formula (3) is a phenylene group or a naphthylene group include the following. In the following examples, a cation having one Te atom-containing group represented by the above formula (1) is shown. However, the Te atom-containing group may have two or more, and the present invention is limited to these. It is not something.
- R 3 of the onium salt compound represented by the above formula (4) is a phenylene group or a naphthylene group include the following. The present invention is not limited to these.
- X ⁇ of the onium salt compound represented by the above formula (2) is an anion.
- Anions such as a sulfonate anion, a carboxylic acid anion, an imide anion, a methide anion, a carbanion, a borate anion, a halogen anion, a phosphate anion, an antimonate anion, an arsenate anion, are mentioned.
- ZA a ⁇ , (Rf) b PF (6-b) ⁇ , R 4 c BA (4-c) ⁇ , R 4 c GaA (4-c) ⁇ , R 5 SO 3 ⁇ , (R 5 SO 2) 3 C - or (R 5 SO 2) 2 N - anion represented by are preferred.
- Two of Rf, two of R 4 and two of R 5 may be bonded to each other to form a ring.
- Z represents a phosphorus atom, a boron atom or an antimony atom.
- A represents a halogen atom (a fluorine atom is preferred).
- P represents a phosphorus atom
- F represents a fluorine atom
- B represents a boron atom
- Ga represents a gallium atom.
- S represents a sulfur atom
- O represents an oxygen atom
- C represents a carbon atom
- N represents a nitrogen atom.
- Rf is preferably an alkyl group in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms, and the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.
- alkyl group to be converted into Rf by fluorine substitution include linear alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl and octyl), branched chain alkyl groups (such as isopropyl, isobutyl, s-butyl and t-butyl) and And cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like.
- the ratio of hydrogen atoms of these alkyl groups substituted by fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90, based on the number of moles of hydrogen atoms that the original alkyl group had. % Or more, particularly preferably 100%.
- the substitution ratio by fluorine atoms is within these preferable ranges, the photosensitivity of the sulfonium salt is further improved.
- Particularly preferred Rf is CF 3 ⁇ , CF 3 CF 2 ⁇ , (CF 3 ) 2 CF ⁇ , CF 3 CF 2 CF 2 ⁇ , CF 3 CF 2 CF 2 CF 2 ⁇ , (CF 3 ) 2 CFCF 2 —. , CF 3 CF 2 (CF 3 ) CF ⁇ and (CF 3 ) 3 C — .
- the b Rf's are independent of each other, and therefore may be the same as or different from each other.
- R 4 represents a phenyl group in which a part of hydrogen atoms is substituted with at least one halogen atom or electron withdrawing group.
- the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
- the electron withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group.
- a phenyl group in which one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable.
- the c R 4 s are independent of each other, and therefore may be the same as or different from each other.
- R 5 represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- the alkyl group and the perfluoroalkyl group are linear or branched. Either a chain or a ring may be used, and the aryl group may be unsubstituted or may have a substituent.
- A represents an integer of 4-6.
- b represents an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3.
- c represents an integer of 1 to 4, and is preferably 4.
- Examples of the anion represented by R 4 c BA (4-c) — include (C 6 F 5 ) 4 B ⁇ , ((CF 3 ) 2 C 6 H 3 ) 4 B ⁇ , (CF 3 C 6 H 4 ) 4 B ⁇ , (C 6 F 5 ) 2 BF 2 ⁇ , C 6 F 5 BF 3 - and (C 6 H 3 F 2) 4 B - anion, and the like represented. Of these, anions represented by (C 6 F 5 ) 4 B — and ((CF 3 ) 2 C 6 H 3 ) 4 B — are preferred.
- Examples of the anion represented by R 4 c GaA (4-c) ⁇ include (C 6 F 5 ) 4 Ga ⁇ , (( CF 3 ) 2 C 6 H 3 ) 4 Ga ⁇ , (CF 3 C 6 H 4 ) 4 Ga ⁇ , (C 6 F 5 ) 2 GaF 2 -, C 6 F 5 GaF 3 - and (C 6 H 3 F 2) 4 Ga - in anion represented the like.
- anions represented by (C 6 F 5 ) 4 Ga ⁇ and ((CF 3 ) 2 C 6 H 3 ) 4 Ga ⁇ are preferable.
- the radiation-sensitive acid generator is preferably a sulfonic acid derivative having an anion structure represented by the following formula (a1), but is not limited thereto.
- R 5a COOCH 2 CH 2 CFHCF 2 SO 3 - (a1)
- R 5a represents a monovalent organic group having 1 to 20 carbon atoms which may have a substituent.
- the organic group is preferably a group represented by the following formula having 1 to 20 carbon atoms.
- L is each independently a direct bond; or —O—, —CO—, —COO—, —OCO—, —O—CO—O—, —NHCO—, —CONH—, —NH—CO—. It is any group selected from the group consisting of O—, —O—CO—NH—, —NH—, —S— and —CO—O—CH 2 —CO—O—.
- R 5c each independently represents a linear, branched or cyclic divalent aliphatic hydrocarbon group; a divalent aromatic hydrocarbon group; and —O—, —CO—, —COO—, — OCO-, -O-CO-O From the group consisting of —, —NHCO—, —CONH—, —NH—CO—O—, —O—CO—NH—, —NH—, —N ⁇ , —S—, —SO— and —SO 2 —.
- m is 0 or an integer of 1 to 10.
- R 5a has the hydroxyl group
- m is 1 or more
- at least one of R 5b and R 5c has the hydroxyl group.
- m is preferably 0 to 5, and more preferably 0 to 3.
- the number of carbon atoms including the number of carbon atoms of the substituent is preferably 1 to 200, more preferably 1 to 100, More preferably, it has 1 to 30 carbon atoms, and particularly preferably 3 to 30 carbon atoms.
- R 5a preferably has a substituent, that is, it is preferable that at least one hydrogen of R 5b and R 5c is substituted with the substituent.
- R 5a may have include a hydroxy group, a carboxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an aryl group, an aryloxy group, a phosphino group, an alkylthio group, and an arylthio group. Yes, but you are not limited to these.
- Examples of the anion represented by R 5 SO 3 — include, in addition to the anion represented by the above formula (a1), a trifluoromethanesulfonic acid anion, a pentafluoroethanesulfonic acid anion, a heptafluoropropanesulfonic acid anion, and a nonafluorobutanesulfonic acid anion.
- trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion and the like can be mentioned.
- Examples of the anion represented by (R 5 SO 2 ) 3 C — include (CF 3 SO 2 ) 3 C ⁇ , (C 2 F 5 SO 2 ) 3 C ⁇ , and (C 3 F 7 SO 2 ) 3 C ⁇ . And an anion represented by (C 4 F 9 SO 2 ) 3 C — and the like.
- Examples of the anion represented by (R 5 SO 2 ) 2 N ⁇ include (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ , and (C 3 F 7 SO 2 ) 2 N ⁇ . And an anion represented by (C 4 F 9 SO 2 ) 2 N — and the like. Moreover, two cyclic imide which parts corresponding to (R 5 SO 2) is bonded to form a ring structure also (R 5 SO 2) 2 N - and the like as the anion represented by.
- monovalent anions include perhalogenate ions (ClO 4 ⁇ , BrO 4 — etc.), halogenated sulfonate ions (FSO 3 ⁇ , ClSO 3 ⁇ etc.), sulfate ions (CH 3 SO 4).
- the low molecular weight component may be added to the resist composition, but may be a polymer contained as a unit. That is, the photosensitive compound represented by the above formula (2) may be included in the polymer as a unit so as to be bonded to the polymer main chain at any position of R 2 of the photosensitive compound.
- the photosensitive compound is an onium salt compound represented by the above formula (2), instead of one H of R 2 , a bond that is bonded to the polymer main chain directly or via a linking group is used. It is preferable to have.
- R 2 has a Te atom-containing group represented by the above formula (1), it is bonded to the polymer main chain directly or via a linking group instead of one H of the Te atom-containing groups. You may have a joint to do.
- the photosensitive compound is a polymer, it may be bonded to the polymer main chain directly or via a linking group at the anion portion instead of the cation portion.
- the unit constituting the polymer a unit derived from a monomer having a radical polymerizable group such as a vinyl group, an isopropenyl group, an acryloxy group and a methacryloxy group is preferable.
- the polymer may be a polymer including units other than the unit corresponding to the metal-containing onium salt compound. Details will be described later.
- the photosensitive compound when a polymer the formula The preferred number of carbon atoms of the R 2 in (2) shall be excluding the number of carbon atoms of the polymer backbone.
- photosensitive compound represented by the above formula (2) examples include those shown below.
- the photosensitive compounds shown below include, but are not limited to, the substitution position corresponding to the -Te-R 1 group.
- the photosensitive compound according to some embodiments of the present invention may be a photosensitive compound having a diazomethane skeleton having the Te atom-containing group.
- the diazomethane skeleton include those having a disulfonyldiazomethane skeleton represented by the following formula (5).
- the diazomethane skeleton may have the Te atom-containing group directly or via a linking group.
- R a1 and R a2 each independently represent a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and Any of an aryl group having 5 to 20 carbon atoms which may have a substituent is shown.
- the hydrocarbon group and aryl group for R a1 and R a2 are preferably selected from the same options as those for R 1 in the above formula (1).
- At least one of R a1 and R a2 contains one or more divalent Te atoms.
- R a1 and R a2 examples include an alkyl group or an alkoxy group having 1 to 4 carbon atoms; an aryl group having 5 to 20 carbon atoms; an aromatic heterocyclic ring having 3 to 5 carbon atoms A nitro group; a halogen atom such as a chlorine atom and a fluorine atom; and the like. Further, it may be a same substituents of the above R 1.
- R a1 and R a2 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, amyl Alkyl groups such as a group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group and adamantyl group; A phenyl group; alkoxyphenyl groups such as p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, pt-butoxyphenyl group, mt-butoxyphenyl group; Alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethyl group
- an alkyl group substituted with a halogen atom such as a trifluoromethyl group, a trifluoroethyl group, a trichloroethyl group and a nonafluorobutyl group;
- a halogen atom such as a trifluoromethyl group, a trifluoroethyl group, a trichloroethyl group and a nonafluorobutyl group
- Preferable examples also include an aryl group substituted with a halogen atom such as a fluorophenyl group, a chlorophenyl group, and a pentafluorophenyl group.
- the photosensitive compound according to some embodiments of the present invention may be a photosensitive compound having an imide skeleton having the Te atom-containing group.
- the imide skeleton include those represented by the following formula (6), and the present invention is not limited to this as long as the imide skeleton has the Te atom-containing group directly or via a linking group.
- R b and R c contains one or more divalent Te atoms.
- R b is a linear, branched or substituted alkyl group having 1 to 8 carbon atoms; an alkenyl group having 2 to 8 carbon atoms; an alkoxyalkyl group having 1 to 8 carbon atoms; a phenyl group or a naphthyl group; An aryl group; Some or all of the hydrogen atoms of these groups may be substituted with a substituent.
- R b may have includes: an alkyl group having 1 to 4 carbon atoms or an alkoxy group; an aryl group having 5 to 20 carbon atoms; an aromatic heterocyclic group having 3 to 5 carbon atoms; Group; halogen atoms such as chlorine atom and fluorine atom; and the like. Further, it may be a same substituents of the above R 1.
- R c is the same as the divalent linking group in the photosensitive compound, and preferably an arylene group having 6 to 10 carbon atoms, or an arylene group having 1 to 6 carbon atoms.
- the substituent that R c may have include an alkyl group having 1 to 4 carbon atoms or an alkoxy group; an aryl group having 5 to 20 carbon atoms; an aromatic heterocyclic group having 3 to 5 carbon atoms; Group; halogen atoms such as chlorine atom and fluorine atom; and the like. Further, it may be a same substituents of the above R 1.
- alkyl group, alkenyl group, and aryl group of R b the same alkyl group and aryl group as R a1 and R a2 of the above formula (5) can also be used.
- alkenyl group for R b include vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1-pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group and 7-octenyl group.
- alkoxyalkyl group for R b examples include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxy Ethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxy A pentyl group, a methoxyhexyl group, a methoxyheptyl group, etc. are mentioned.
- arylene group for R c 1,2-phenylene group, 1,8-naphthylene group and the like, and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group and norbornane-2, Examples include 3-diyl group.
- alkenylene group include a 1,2-vinylene group, a 1-phenyl-1,2-vinylene group, and a 5-norbornene-2,3-diyl group.
- imide skeleton examples include, but are not limited to, the following.
- the photosensitive compound according to some embodiments of the present invention may be a photosensitive compound having an oxime skeleton having the Te atom-containing group.
- the oxime skeleton include those represented by the following formula (7), and the present invention is not limited to this as long as the oxime skeleton has the Te atom-containing group directly or via a linking group.
- At least one of R d1 , R d2 and R e contains one or more divalent Te atoms. It is preferable that at least one of R d1 and R d2 has at least one electron-withdrawing group such as a cyano group and a fluorinated alkyl group.
- R d1 and R d2 are each independently preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group, and a cyano group, which may have a substituent. Some or all of the hydrogen atoms of these groups may be substituted with a substituent.
- Examples of the alkyl group and aryl group of R d1 and R d2 include the same alkyl group and aryl group as R 1 in the above formula (1).
- Examples of the substituent that R d1 and R d2 may have include an alkyl group or alkoxy group having 1 to 4 carbon atoms; an aryl group having 5 to 20 carbon atoms; an aromatic heterocyclic ring having 3 to 5 carbon atoms A nitro group; a halogen atom such as a chlorine atom and a fluorine atom; and the like. Further, it may be a same substituents of the above R 1.
- R e examples include the same as R b in the above formula (6).
- R e represents a linear, branched or substituted alkyl group; an alkenyl group; an alkoxyalkyl group; an aryl group such as a phenyl group or a naphthyl group; Some or all of the hydrogen atoms of these groups may be substituted with a substituent.
- the substituent which R e may have include an alkyl group having 1 to 4 carbon atoms or an alkoxy group; an aryl group having 5 to 20 carbon atoms; an aromatic heterocyclic group having 3 to 5 carbon atoms; Group; halogen atoms such as chlorine atom and fluorine atom; and the like. Further, it may be a same substituents of the above R 1.
- the alkyl group for R e preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, and the number of carbon atoms 1-4 are most preferred.
- a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable.
- the partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms.
- halogen atom means an alkyl group substituted with Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
- the aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
- a partially or completely halogenated aryl group is particularly preferable.
- the partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms.
- R d1 and R d2 may be bonded to each other to form a ring.
- the photosensitive compound according to some embodiments of the present invention is not particularly limited as long as it has the Te atom-containing group.
- onium salts such as phosphonium salts, ammonium salts, and pyridinium salts; glyoxime compounds; It may be in the form of a sulfone compound such as a bissulfonic acid compound, a ⁇ -ketosulfonic acid compound and a disulfonic acid compound; a sulfonic acid ester or the like.
- the photosensitive compound of some aspects of the present invention can be used as a component of a resist composition alone or in combination of two or more.
- the photosensitive compound in some embodiments of the present invention is suitably used as a photoacid generator, a photodegradable base, a sensitizer and the like. In particular, it is preferably used as a photoacid generator and a photodisintegrable base.
- the photosensitive compound in some embodiments of the present invention may be a polymer.
- the photosensitive compound is a polymer
- the polymer may be a homopolymer as long as it includes a unit that functions as a photosensitive compound, or may be a copolymer that includes other units.
- other units include those that act as acid-reactive compounds and hydroxyaryl group-containing units. What acts as the acid-reactive compound and the hydroxyaryl group-containing unit will be described later.
- the photosensitive compound in one embodiment of the present invention can be synthesized by the following method.
- the synthesis example of the sulfonium salt whose Y is a sulfur atom in the said Formula (2) is shown.
- magnesium is added to THF and heated to 40 to 50 ° C.
- a tetrahydrofuran (THF) solution of a sulfide compound having —R 2a group and —R 2b —Br group is added dropwise thereto.
- THF tetrahydrofuran
- tellurium-containing sulfide is oxidized to sulfoxide using MCPBA or the like, tellurium-containing sulfonium chloride salt is obtained by Grignard reaction. Thereafter, a tellurium-containing sulfonium salt compound having a corresponding X- can be obtained by salt exchange or the like.
- the tellurium-containing sulfide is reacted with iodonium methylsulfate having a —R 2c group to obtain tellurium-containing sulfonium methylsulfate, and then a tellurium-containing sulfonium salt compound having the corresponding X ⁇ is obtained by salt exchange or the like.
- R 2a and R 2c are selected from the same options as R 1 above.
- R 2b is selected from the same options as R 3 above.
- Y is an iodine atom
- Y it can be synthesized as follows. First, 1-bromo-4-iodobenzene, trifluoromethanesulfonic acid, benzene and dichloromethane are mixed. The MCPBA dichloromethane solution is dropped here and reacted to give 4-bromophenylphenyliodonium trifluoromethanesulfonate. Next, a THF solution of 4-bromophenylphenyl iodonium trifluoromethanesulfonate is added dropwise to the THF solution of magnesium.
- a THF solution of an organic tellurium compound having an R 1 group is dropped and reacted by a Grignard reaction to obtain tellurium-containing iodonium.
- a tellurium-containing iodonium salt compound having a corresponding X- can be obtained by salt exchange or the like.
- Resist Composition One aspect of the present invention relates to a resist composition containing the photosensitive compound.
- the said resist composition can use the said photosensitive compound as a component of a resist composition in combination with any of a photo-acid generator, a photodegradable base, and a sensitizer.
- the anion of the photodegradable base has a lower acid strength than the anion of the photoacid generator It is preferable to use them in appropriate combinations.
- the photoacid generator preferably has a pKa of ⁇ 3 or less. Examples of such anions include fluorine-substituted sulfonic acid.
- pKa is a value obtained by analysis using ACD labs (manufactured by Fujitsu Limited).
- a photoacid generator other than the photosensitive compound of some embodiments of the present invention and a photodegradable base may further be included.
- the resist composition preferably further contains an acid-reactive compound.
- the resist composition of some embodiments of the present invention may be used as a photoacid generator (hereinafter referred to as “second photoacid generator”). May also be included.
- a second photoacid generator is not particularly limited as long as it is used in a normal resist composition.
- onium salt compounds such as sulfonium salts and iodonium salts, N-sulfonyloxyimide compounds, Examples thereof include oxime sulfonate compounds, organic halogen compounds, and sulfonyldiazomethane compounds. These can be used individually by 1 type or in combination of 2 or more types. Examples of the sulfonium salt include those described in WO2011 / 093139.
- the second photoacid generator may be added to the resist composition as a low molecular weight component, but may be contained as a polymer unit. That is, the aspect contained in the polymer as a unit so that it may couple
- the photoacid generator is a sulfonium salt
- the total content of the photoacid generator (including the second photoacid generator) in the resist composition of one embodiment of the present invention is 1 to 50 in total with respect to 100 parts by mass of the acid-reactive compound described later.
- the amount is preferably 3 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 5 to 25 parts by mass.
- the mass is based on the polymer main chain.
- the resist composition of one embodiment of the present invention may contain other photodegradable base.
- the photodegradable base the same cations as those of the other photoacid generators can be used. At that time, it is preferable to use an anion having a smaller acid strength than the anion of the photoacid generator.
- the content of the photodegradable base in the resist composition is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the acid-reactive compound described later. It is preferably 2 to 25 parts by mass. Further, the content of the photodegradable base in the resist composition is preferably 1 to 50 parts by mass, more preferably 3 to 25 parts by mass with respect to 10 parts by mass of the photoacid generator.
- the organic solvent is not included in the resist composition component.
- bonds with a polymer it is set as the mass reference
- the resist composition according to some embodiments of the present invention preferably contains an acid-reactive compound.
- the acid-reactive compound preferably has a protecting group that is deprotected with an acid, is polymerized with an acid, or is crosslinked with an acid. That is, the acid-reactive compound is at least one selected from the group consisting of a compound having a protecting group that is deprotected by an acid, a compound having a polymerizable group that is polymerized by an acid, and a crosslinking agent having a crosslinking action by an acid. It is preferable that
- the compound having a protecting group that is deprotected by an acid is a compound that generates a polar group by deprotecting the protecting group with an acid and changes its solubility in a developing solution.
- a compound having a protecting group that is deprotected by an acid is insoluble in an alkali developer, but in an exposed area by an acid generated from the photoacid generator upon exposure. It is a compound that becomes soluble in an alkaline developer when the protecting group is deprotected from the compound.
- the developer is not limited to an alkaline developer, and may be a neutral developer or an organic solvent development. Therefore, when an organic solvent developer is used, a compound having a protecting group that is deprotected with an acid is polarized by deprotecting the protecting group from the compound in the exposed area by an acid generated from the photoacid generator upon exposure. It is a compound that generates a group and has a reduced solubility in an organic solvent developer.
- the polar group examples include a hydroxy group, a carboxy group, an amino group, and a sulfo group.
- the protecting group to be deprotected with an acid examples include an ester group, an acetal group, a tetrahydropyranyl group, a carbonate group, a siloxy group, and a benzyloxy group.
- the compound having the protecting group a compound having a styrene skeleton, a methacrylate or an acrylate skeleton pendant with these protecting groups is preferably used.
- the compound having a protecting group to be deprotected with an acid may be a protecting group-containing low molecular weight compound or a protecting group-containing polymer.
- the low molecular weight compound has a weight average molecular weight of less than 2000
- the polymer has a weight average molecular weight of 2000 or more.
- the compound having a polymerizable group that is polymerized with an acid is a compound that changes the solubility in a developer by polymerizing with an acid. For example, in the case of aqueous development, it acts on a compound that is soluble in an aqueous developer and lowers the solubility of the compound in the aqueous developer after polymerization.
- Specific examples include compounds having an epoxy group, a vinyloxy group, an oxetanyl group, and the like.
- the compound having a polymerizable group that is polymerized with an acid may be a polymerizable low-molecular compound or a polymerizable polymer.
- a crosslinking agent having a crosslinking action with an acid is a compound that changes the solubility in a developer by crosslinking with an acid. For example, in the case of aqueous development, it acts on a compound that is soluble in an aqueous developer, and lowers the solubility of the compound in the aqueous developer after polymerization or crosslinking.
- Specific examples include crosslinking agents having an epoxy group, a vinyloxy group, a 1-alkoxyamino group, an oxetanyl group, and the like.
- examples of the cross-linking partner compound that is, a compound that reacts with the cross-linking agent and changes its solubility in a developing solution include compounds having a phenolic hydroxyl group.
- the compound having a crosslinking action with an acid may be a polymerizable low molecular compound or a polymerizable polymer.
- the polymer may contain other units usually used in the resist composition in addition to the unit to which the reactive compound is bonded.
- other units include a unit (I) having at least one skeleton selected from the group consisting of a lactone skeleton, a sultone skeleton, a lactam skeleton, and the like; a group having an ether bond, an ester bond, and an acetal structure; and And unit (II) having at least one group selected from the group consisting of a hydroxy group and the like; a hydroxyaryl group-containing unit (III); and the like.
- the ratio of each unit of the polymer is not particularly limited, but when the unit to which the acid-reactive compound is bonded is included as a unit of the same polymer together with other units, the acid reaction
- the unit to which the active compound is bonded is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, and still more preferably 20 to 60 mol% in the total polymer unit.
- the unit (I) is preferably from 0 to 60 mol%, more preferably from 10 to 60 mol%, still more preferably from 20 to 60 mol%.
- the unit (II) is preferably from 0 to 70 mol%, more preferably from 5 to 70 mol%, still more preferably from 10 to 60 mol%.
- the unit (III) is preferably 0 to 90 mol%, more preferably 10 to 80 mol% of the whole.
- the unit (IV) is preferably 0 to 30 mol%, more preferably 1 to 30 mol%, and further preferably 3 to 20 mol%.
- the unit (V) is preferably 0 to 30 mol%, more preferably 1 to 30 mol%, still more preferably 3 to 20 mol%.
- the polymer can be synthesized, for example, as follows.
- the monomer constituting each unit can be obtained by polymerizing by a known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN) and dimethyl azobisisobutyrate.
- a chain transfer agent such as HS—CH 2 —CH 2 —CH 2 —C (CF 3 ) 2 —OH is used in combination, and a —C (CF 3 ) 2 —OH group is attached to the polymer terminal. May be introduced.
- a polymer into which a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom is effective for reducing development defects and LER.
- an organic solvent In the resist composition of one embodiment of the present invention, an organic solvent, an acid diffusion controller, a surfactant, an organic carboxylic acid, and a dissolution inhibitor used in a normal resist composition as optional components other than the above components as necessary.
- Stabilizers, dyes and sensitizers may be included in combination.
- organic solvent examples include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether.
- PGME propylene glycol monomethyl ether
- PGMEA propylene glycol monomethyl ether acetate
- propylene glycol monomethyl ether propionate propylene glycol monoethyl ether.
- the acid diffusion control agent controls the diffusion phenomenon of the acid generated from the photoacid generator in the resist film, and has an effect of controlling an undesirable chemical reaction in the non-exposed region. Therefore, the storage stability of the resulting resist composition is further improved, the resolution as a resist is further improved, and changes in the line width of the resist pattern due to fluctuations in the holding time from exposure to development processing can be suppressed. Thus, a resist composition having excellent process stability can be obtained.
- the acid diffusion controller include a compound having one nitrogen atom in the same molecule, a compound having two, a compound having three nitrogen atoms, an amide group-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound. It is done.
- the photodegradable base other than the metal-containing onium salt compound according to one embodiment of the present invention that is exposed to light upon exposure to generate a weak acid can be used.
- the acid diffusion control agent is included, the content thereof is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 15 parts by mass with respect to 100 parts by mass of the acid-reactive compound. 0.05 to 10 parts by mass is more preferable. The content does not include the photodegradable base.
- the surfactant is preferably used for improving the coating property.
- surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Agents, fluorosurfactants, organosiloxane polymers, and the like.
- the content of the surfactant is preferably 0.0001 to 2 parts by mass, more preferably 0.0005 to 1 part by mass with respect to 100 parts by mass of the acid-reactive compound.
- organic carboxylic acid examples include aliphatic carboxylic acid, alicyclic carboxylic acid, unsaturated aliphatic carboxylic acid, oxycarboxylic acid, alkoxycarboxylic acid, ketocarboxylic acid, benzoic acid derivative, phthalic acid, terephthalic acid, isophthalic acid, 2 -Naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid and the like.
- preferred organic carboxylic acids include aromatic organic carboxylic acids, among which, for example, benzoic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid are preferred.
- the content of the organic carboxylic acid is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the acid-reactive compound. Part by mass.
- the resist composition component is preferably dissolved in the organic solvent and dissolved at a solid content concentration of 1 to 40% by mass. More preferably, it is 1 to 30% by mass, and further preferably 3 to 20% by mass.
- the polymer When the resist composition of one embodiment of the present invention contains a polymer, the polymer preferably has a weight average molecular weight of 2,000 to 200,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 15,000. .
- the polymer preferably has a dispersity (molecular weight distribution) (Mw / Mn) of 1.0 to 2.2, more preferably 1.2 to 2.0 from the viewpoint of sensitivity.
- the polymer weight average molecular weight and degree of dispersion are defined as polystyrene equivalents by GPC measurement.
- the resist composition of one embodiment of the present invention may contain a fluorine-containing water-repellent polymer.
- a fluorine-containing water-repellent polymer Although there is no restriction
- the fluorine content of the fluorine water-repellent polymer is preferably such that 25% or more of the hydrogen atoms in the hydrocarbon groups in the fluorine water-repellent polymer are fluorinated, more preferably 50% or more. preferable.
- the content of the fluorine water-repellent polymer in the resist composition is 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer of the embodiment of the present invention (which is not the fluorine water-repellent polymer). It is preferable from the viewpoint of improving the hydrophobicity of the resist film.
- a fluorine water-repellent polymer may be used independently and may be used in combination of 2 or more types.
- composition of one embodiment of the present invention can be obtained by mixing the components of the above composition, and the mixing method is not particularly limited.
- One embodiment of the present invention includes a step of forming a resist film by, for example, applying the resist composition on a substrate, a step of exposing the resist film, and an exposed resist film. And developing a resist pattern to form a resist pattern.
- One embodiment of the present invention is a method for producing a substrate having a pattern before obtaining individualized chips, including a step of forming a resist film and a step of forming a pattern using the resist composition. Also good.
- the active energy ray used for the exposure in the exposure step may be any light or particle beam that can activate the photosensitive compound of one embodiment of the present invention to generate an acid, such as a KrF excimer laser beam or an ArF excimer laser beam. , F 2 excimer laser light, i-line and other UV, visible light, X-ray, electron beam, ion beam, EUV and the like.
- an active energy ray used for exposure in the exposure step is preferably an electron beam (EB) or extreme ultraviolet (EUV).
- the amount of light irradiation varies depending on the type and blending ratio of each component in the photocurable composition, the film thickness of the coating film, and the like, but is preferably 1 J / cm 2 or less or 1000 ⁇ C / cm 2 or less.
- the resist composition contains the sensitizer or the polymer contains the corresponding sensitizer as a sensitizer unit, the resist composition is subjected to a second exposure with UV or the like after the first exposure with an electron beam or EUV. It is also preferable to do this.
- Synthesis Example 7 Synthesis of Tellurium-Containing Sulfonium Salt 4
- 4-bromophenylphenyl sulfide was used instead of 2-bromodibenzothiophene, and in Synthesis Example 4, sodium-4-butane was substituted for potassium nonafluorobutanesulfonate.
- Synthesis is performed in the same manner as in Synthesis Examples 1 to 4, except that (3-hydroxy-1-adamantanecarbonyloxy) 1,1,2-trifluorobutane-1-sulfonate is used.
- ⁇ Preparation of resist composition 100 parts by mass of each of polymer (A-1), polymer (A-2) and polymer (A-3) as a base polymer, and 8 parts by mass of tellurium-containing sulfonium salt 1 as a photoacid generator Then, 1800 parts by mass of propylene glycol monomethyl ether acetate as a solvent was mixed, and then filtered through a PTFE filter to prepare a resist composition (H-1) solution. Details of the resist composition are shown in Table 1.
- Examples 2 to 12 In the same manner as in Example 1, except that any one of the tellurium-containing sulfonium salts 2 to 4 synthesized above was used as a photoacid generator instead of the tellurium-containing sulfonium salt 1 in the amount shown in Table 1, a resist composition ( H-2) to (H-12) are obtained. [Comparative Examples 1 to 12]
- Example 1 except that any one of the photoacid generators (B-1) to (B-4) was used in the blending amount shown in Table 1 instead of the tellurium-containing sulfonium salt 1 as the photoacid generator, Resist compositions (H-13) to (H-24) are obtained.
- the photoacid generators (B-1) to (B-4) are shown below.
- Each resist composition was spin-coated on a silicon wafer by a spin coater and then pre-baked on a hot plate at 110 ° C. for 60 seconds to obtain a coating film having a thickness of 150 nm.
- a mask so as to obtain a 90 nm line pattern exposure is performed with an ArF excimer laser, and then post-baking is performed at 110 ° C. for 90 seconds. Thereafter, development is performed for 60 seconds using an aqueous 2.38 mass% tetramethylammonium hydroxide solution, and then rinsed with pure water for 30 seconds to obtain a patterned substrate.
- the resolution, focus depth and line edge roughness at this time are based on the values of Comparative Example 1, and the sensitivity, resolution, depth of focus and focus of Examples 1 to 12 and Comparative Examples 2 to 12 are compared with the reference.
- Each performance of line edge roughness is evaluated using the following as an index.
- a scanning electron microscope is used for measuring the resist pattern.
- ⁇ When improvement of 10% or more is observed with respect to Comparative Example 1.
- X When the improvement is less than 5% with respect to Comparative Example 1.
- (Resolution) The width (nm) of the line pattern that can be resolved with the minimum exposure amount that reproduces the 90 nm line pattern, that is, the limiting resolution is shown. The smaller the numerical value, the better the resolution.
- (Depth of focus) The range of acceptable focus that can reproduce the 90 nm line pattern when the focus position is moved up and down, exposure is performed with the minimum exposure to reproduce the 90 nm pattern on the mask, and post-baking (PEB) and development are performed. Indicates. The larger the focus range, the smaller and better the pattern dimension change with respect to the focus depth change.
- Line edge roughness For the range of 2.5 ⁇ m edge in the longitudinal direction of the 90 nm line pattern obtained with the minimum exposure to reproduce the 90 nm line pattern, measure the distance from the reference line where the edge should be 50 points, and calculate the standard deviation ( ⁇ ) The triple value (3 ⁇ ) was calculated as LER. The smaller the value, the smaller the roughness and the more uniform pattern edge is obtained.
- a resist composition (H-27) is obtained in the same manner as in Example 13 except that no tellurium-containing sulfonium salt is added.
- the total molar amounts used of the photoacid generator represented by the above formula (B-5) and the tellurium-containing sulfonium salt 1 are the same.
- ⁇ Sensitivity evaluation> Each resist composition is spin-coated on a silicon wafer by a spin coater and then pre-baked on a hot plate at 110 ° C. for 60 seconds to obtain a coating film having a thickness of 50 nm. It was exposed by EUV, and then post-baked at 110 ° C. for 60 seconds. Thereafter, development is performed for 60 seconds using an aqueous 2.38 mass% tetramethylammonium hydroxide solution, and then rinsed with pure water for 30 seconds to obtain a patterned substrate. At this time, the exposure amount at which the remaining film of the formed resist film becomes 0 is evaluated as sensitivity.
- Examples 1 to 12 using the tellurium-containing sulfonium salt of some aspects of the present invention are excellent in resolution, depth of focus and LER characteristics.
- Comparative Examples 1 to 12 that do not use the tellurium-containing sulfonium salt problems remain in resolution, depth of focus, and LER characteristics.
- Examples 13 and 14 and Comparative Example 13 it can be seen that in sensitivity evaluation, an increase in sensitivity can be obtained by mixing an appropriate amount of the tellurium-containing sulfonium salt with the photoacid generator.
- any one of the photoacid generators (B-1) to (B-4) may be combined with the tellurium-containing sulfonium salt. Also when used together, the same results as in Examples 13 and 14 are obtained. From the above results, it can be seen that the photosensitive compound according to one aspect of the present invention is excellent in sensitivity, resolution, and depth of focus in lithography, and has an effect of reducing LER in a fine pattern.
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Abstract
Description
一方、従来のEUVリソグラフィ装置では、光源からレーザを照射するのに必要なパワーが十分でなく、露光時にレジスト組成物中の光酸発生剤から効率よく酸を発生させるためにドーズを大きくするのには限界がある。そのため、レジスト組成物における光酸発生剤の酸発生効率の向上が求められている。
特に、従来の電子線又はEUV等用の化学増幅型レジスト組成物は、電子線又はEUVの吸収が小さく、電子線又はEUVに対する感度、解像度、焦点深度及びパターン性能の特性を同時に満たすことは難しい。
また本発明のいくつかの態様は、上記感光性化合物、それを含む光酸発生剤及びレジスト組成物、並びに、上記レジスト組成物を用いたデバイスの製造方法を提供することを課題とする。
より具体的には、オニウム塩骨格、ジアゾメタン骨格、イミド骨格及びオキシム骨格から選択されるいずれかの骨格を有し、上記骨格が下記式(1)で表されるTe原子含有基を少なくとも1つ有する感光性化合物である。
さらに、本発明の別の態様は、上記レジスト組成物を用いて基板上にレジスト膜を形成する工程と、上記レジスト膜を露光する工程と、露光された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、を含むデバイスの製造方法である。
<1>感光性化合物
本発明のひとつの態様の感光性化合物は、2価のTe原子を含有する。
上記感光性化合物は、2価のTe原子を含有することで、KrF等の波長の短い光、特にEUV又は電子線等に対する膜吸収が増大し、イオン化される効率が高く2次電子発生効率が上がる。そのため、上記感光性化合物を含有するレジスト組成物は高感度となることが考えられる。
上記Te原子含有基は直接上記骨格と結合していてもよく、また、2価の連結基を介して結合していてもよい。2価の連結基としては、直鎖、分岐又は環状の2価の炭化水素基;アリーレン基;及びこれらの基が酸素原子、硫黄原子又は窒素原子含有基を介して結合した基等が挙げられる。上記2価の炭化水素基は、R1の炭化水素基から水素を一つとって2価になったものが挙げられる。上記アリーレン基は、R1のアリール基から水素を一つとって2価になったものが挙げられる。
イソプロピル及びt-ブチル等の分岐状アルキル基;
シクロブチル基、シクロペンチル基及びシクロヘキシル基等の環状アルキル基;並びに、上記アルキル基の少なくとも1つの炭素-炭素一重結合が炭素-炭素二重結合に置換されたアルケニル基;
上記アルキル基の炭素-炭素一重結合の少なくとも1つが炭素-炭素三重結合に置換されたアルキニル基;等を挙げることができる。
上記ヘテロ原子含有基を含む炭化水素基としては、例えば、アルコキシ基;アルキルカルボニルオキシ基;ラクトン構造、スルトン構造及びラクタム構造等のヘテロ環構造を有する炭化水素基;等が挙げられる。
上記ArSpとしては、フェニル基及びナフチル基等の炭素原子数12以下の芳香族炭化水素基、並びに環構造中に炭素原子に代えてヘテロ原子を含んでいても良い芳香族複素環基が挙げられる。置換基としてのアルキル基(RSp)、アルケニル基及びアリール基(ArSp)としては、上記R1の上記アルキル基、上記アルケニル基及び上記アリール基と同様のものが挙げられる。
R1の置換基としてのハロゲン原子としては、フッ素原子、塩素原子及び臭素原子等が挙げられる。
なお、R1が置換基を有する場合の各R1の総炭素原子数は、置換基を含めて1~20であることが好ましく、5~15であることがさらに好ましく、6~10であることが特に好ましい。
R1の置換基としてはメチル基等のアルキル基、アルコキシ基、ヒドロキシ基及びアリール基等が好ましい。
R1としては、メチル基及びn-ブチル基等のアルキル基、並びに、フェニル基及びナフチル基等のアリール基等が好ましい。
本発明のいくつかの態様の感光性化合物が、オニウム塩骨格を有する場合、例えば、下記式(2)で表されるものが挙げられる。しかし、本発明はこれに限定されない。
R2は、それぞれ独立して上記R1と同じ選択肢から選択され、且つ、上記式(2)中、R2の少なくとも1つは、上記Te原子含有基を置換基として有する。
R2の置換基としては、R1の置換基と同様のものが挙げられる。
R2の置換基として好ましくは、アルキル基、エステル基、ヒドロキシ基、スルホニル基、フルオロ基等が挙げられる。
R2が上記Te原子含有基を有する場合、好ましいR2としては、膜密度及び溶解性等の点から、上記Te原子含有基を有するアリール基が好ましく、該アリール基の中でも上記Te原子含有基を有するフェニル基及び上記Te原子含有基を有するナフチル基等がより好ましい。
R2が上記Te原子含有基を有しない場合、好ましいR2としては、溶解性等の点から、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基、シクロペンチル基、シクロヘキシル基及びアダマンチル基等のアルキル基、並びに、アリール基等が挙げられる。
R2のうちいずれか2つ以上が互いに結合してこれらが結合してYと共に環構造を形成しているカチオンとしては、例えば下記が挙げられる。下記においてはYは硫黄原子、セレン原子及びテルル原子のいずれかとする。なお、-R3-Te-R1は、上記式(1)で表されるTe原子含有基を有するR2に対応する。。下記例示において、上記Te原子含有基を1つ有するカチオンを示したが、該Te原子含有基は2つ以上有していてもよく、本発明においては下記例示に限定されない。上記R3としては上記連結基等が挙げられる。
本発明のいくつかの態様の感光性化合物は、上記式(1)で表されるTe原子含有基を2つ以上有することが電子線又はEUVに対する吸収が高くなることから好ましい。
これについても下記例示において、上記式(1)で表されるTe原子含有基を1つ有するカチオンを示したが、該Te原子含有基は2つ以上有していてもよく、本発明においては下記例示に限定されない。
上記式(3)又は(4)で表されるオニウム塩化合物のカチオンはモノカチオンを示しているが、ポリカチオンであってもよく、ポリカチオンであるときのアニオンはそれに対応するものとする。
上記式(3)で表されるオニウム塩化合物のR3がフェニレン基又はナフチレン基である場合の具体的な構造としては、下記に示すものが挙げられる。下記例示において、上記式(1)で表されるTe原子含有基を1つ有するカチオンを示したが、該Te原子含有基は2つ以上有していてもよく、本発明はこれらに限定されるものではない。
より詳しくは、アニオンとして、ZAa-、(Rf)bPF(6-b) -、R4 cBA(4-c) -、R4 cGaA(4-c) -、R5SO3 -、(R5SO2)3C-又は(R5SO2)2N-で表されるアニオンが好ましく挙げられる。Rfの2個、R4の2個及びR5の2個はそれぞれ、互いに結合して環を形成してもよい。
Zは、リン原子、ホウ素原子又はアンチモン原子を表す。Aはハロゲン原子(フッ素原子が好ましい。)を表す。
Pはリン原子、Fはフッ素原子、Bはホウ素原子、Gaはガリウム原子を表す。
Sはイオウ原子、Oは酸素原子、Cは炭素原子、Nは窒素原子を表す。
フッ素原子による置換割合がこれら好ましい範囲にあると、スルホニウム塩の光感応性がさらに良好となる。特に好ましいRfとしては、CF3 -、CF3CF2 -、(CF3)2CF-、CF3CF2CF2 -、CF3CF2CF2CF2 -、(CF3)2CFCF2 -、CF3CF2(CF3)CF-及び(CF3)3C-が挙げられる。b個のRfは、相互に独立であり、従って、互いに同一でも異なっていてもよい。
-、(CF3CF2)3PF3 -、((CF3)2CF)2PF4 -、((CF3)2C
F)3PF3 -、(CF3CF2CF2)2PF4 -、(CF3CF2CF2)3PF3
-、((CF3)2CFCF2)2PF4 -、((CF3)2CFCF2)3PF3 -、
(CF3CF2CF2CF2)2PF4 -及び(CF3CF2CF2CF2)3PF3 -
で表されるアニオン等が挙げられる。これらのうち、(CF3CF2)3PF3 -、(CF3CF2CF2)3PF3 -、((CF3)2CF)3PF3 -、((CF3)2CF)2PF4 -、((CF3)2CFCF2)3PF3 -及び((CF3)2CFCF2)
2PF4 -で表されるアニオンが好ましい。
3)2C6H3)4B-、(CF3C6H4)4B-、(C6F5)2BF2 -、C6F
5BF3 -及び(C6H3F2)4B-で表されるアニオン等が挙げられる。これらのうち、(C6F5)4B-及び((CF3)2C6H3)4B-で表されるアニオンが好ましい。
CF3)2C6H3)4Ga-、(CF3C6H4)4Ga-、(C6F5)2GaF2
-、C6F5GaF3 -及び(C6H3F2)4Ga-で表されるアニオン等が挙げられ
る。これらのうち、(C6F5)4Ga-及び((CF3)2C6H3)4Ga-で表されるアニオンが好ましい。
上記式(a1)において、R5aは、置換基を有していてもよい炭素原子数1~20の1価の有機基を示す。上記有機基として、好ましくは、炭素原子数1~20の下記式で表される基が挙げられる。
R5b-(L-R5c)m- (a2)
また、Lは、各々独立に、直接結合;又は-O-、-CO-、-COO-、-OCO-、-O-CO-O-、-NHCO-、-CONH-、-NH-CO-O-、-O-CO-NH-、-NH-、-S-及び-CO-O-CH2-CO-O-からなる群より選ばれる
いずれかの基である。
R5cは、各々独立に、直鎖状、分岐状又は環状の2価の脂肪族炭化水素基;2価の芳香族炭化水素基;並びに、-O-、-CO-、-COO-、-OCO-、-O-CO-O
-、-NHCO-、-CONH-、-NH-CO-O-、-O-CO-NH-、-NH-、-N=、-S-、-SO-及び-SO2-からなる群より選ばれる少なくとも1種の基
を骨格に含む2価の脂肪族複素環基又は2価の芳香族複素環基;より選ばれるいずれかの2価の基である。
なお、R5aが置換基を有している場合、その置換基の炭素原子数も含めて、炭素原子数1~200であることが好ましく、炭素原子数1~100であることがより好ましく、炭素原子数1~30であることがさらに好ましく、炭素原子数3~30であることが特に好ましい。また、R5aが置換基を有していることが好ましく、すなわち、R5b及びR5cが有する少なくとも1つの水素が該置換基で置換されていることが好ましい。
R5aが有していてもよい上記置換基としては、ヒドロキシ基、カルボキシル基、アルコキシ基、アシル基、アルコキシカルボニル基、アリール基、アリーロキシ基、ホスフィノ基、アルキルチオ基及びアリールチオ基等を挙げることができるが、これらに制限されない。
R5SO3 -で表されるアニオンとしては、上記式(a1)に示すアニオン以外に、トリフルオロメタンスルホン酸アニオン、ペンタフルオロエタンスルホン酸アニオン、ヘプタフルオロプロパンスルホン酸アニオン、ノナフルオロブタンスルホン酸アニオン、ペンタフルオロフェニルスルホン酸アニオン、p-トルエンスルホン酸アニオン、ベンゼンスルホン酸アニオン、カンファースルホン酸アニオン、メタンスルホン酸アニオン、エタンスルホン酸アニオン、プロパンスルホン酸アニオン及びブタンスルホン酸アニオン等が挙げられる。これらのうち、トリフルオロメタンスルホン酸アニオン、ノナフルオロブタンスルホン酸アニオン、メタンスルホン酸アニオン、ブタンスルホン酸アニオン、ベンゼンスルホン酸アニオン及びp-トルエンスルホン酸アニオン等が挙げられる。
るアニオン等が挙げられる。
るアニオン等が挙げられる。また、2つの(R5SO2)に対応する部分が互いに結合して環構造を形成した環状イミドも(R5SO2)2N-で表されるアニオンとして挙げられる。
ポリマーを構成するユニットとしては、ビニル基、イソプロペニル基、アクリルオキシ基及びメタクリルオキシ基等のラジカル重合性基を有するモノマー由来のユニットが好ましい。上記ポリマーは、上記金属含有オニウム塩化合物に対応するユニット以外の他のユニットを含むポリマーであってもよい。詳しくは後述する。
なお、上記感光性化合物がポリマーであるとき、上記式(2)における上記R2の好ましい炭素原子数は、ポリマー主鎖の炭素原子数を除いたものとする。
本発明のいくつかの態様の感光性化合物は、上記Te原子含有基を有するジアゾメタン骨格を有する感光性化合物であってもよい。ジアゾメタン骨格としては、例えば下記式(5)で表されるジスルホニルジアゾメタン骨格を有するものが挙げられる。該ジアゾメタン骨格が直接又は連結基を介して上記Te原子含有基を有していればよい。
Ra1又はRa2の少なくとも一方に2価のTe原子を1つ以上含む。
Ra1及びRa2が有してもよい置換基としては、炭素原子数1~4のアルキル基又はアルコキシ基;炭素原子数5~20のアリール基;炭素原子数3~5の芳香族複素環基;ニトロ基;塩素原子及びフッ素原子等のハロゲン原子;等が挙げられる。また、上記R1の置換基と同様の置換基であってもよい。
フェニル基;
p-メトキシフェニル基、m-メトキシフェニル基、o-メトキシフェニル基、エトキシフェニル基、p-t-ブトキシフェニル基、m-t-ブトキシフェニル基等のアルコキシフェニル基;
2-メチルフェニル基、3-メチルフェニル基、4-メチルフェニル基、エチルフェニル基、4-t-ブチルフェニル基、4-ブチルフェニル基、ジメチルフェニル基等のアルキルフェニル基;
芳香族複素環基;
ベンジル基、フェネチル基等のアラルキル基;等が挙げられる。
また、トリフルオロメチル基、トリフルオロエチル基、トリクロロエチル基及びノナフルオロブチル基等のハロゲン原子で置換されたアルキル基;
フルオロフェニル基、クロロフェニル基、ペンタフルオロフェニル基等のハロゲン原子で置換されたアリール基等も好ましく挙げられる。
本発明のいくつかの態様の感光性化合物は、上記Te原子含有基を有するイミド骨格を有する感光性化合物であってもよい。イミド骨格としては、下記式(6)で表されるものが挙げられ、イミド骨格が直接又は連結基を介して上記Te原子含有基を有していれば、本発明はこれに限定されない。
Rbは炭素原子数1~8の直鎖状、分岐状若しくは置換のアルキル基;炭素原子数2~8のアルケニル基;炭素原子数1~8のアルコキシアルキル基;フェニル基又はナフチル基等のアリール基;等を示す。これらの基の水素原子の一部又は全部が置換基で置換されていてもよい。
Rbが有してもよい置換基としては、炭素原子数1~4のアルキル基又はアルコキシ基;炭素原子数5~20のアリール基;炭素原子数3~5の芳香族複素環基;ニトロ基;塩素原子及びフッ素原子等のハロゲン原子;等が挙げられる。また、上記R1の置換基と同様の置換基であってもよい。
Rcが有してもよい置換基としては、炭素原子数1~4のアルキル基又はアルコキシ基;炭素原子数5~20のアリール基;炭素原子数3~5の芳香族複素環基;ニトロ基;塩素原子及びフッ素原子等のハロゲン原子;等が挙げられる。また、上記R1の置換基と同様の置換基であってもよい。
Rbのアルケニル基としては、ビニル基、1-プロペニル基、アリル基、1-ブテニル基、3-ブテニル基、イソプレニル基、1-ペンテニル基、3-ペンテニル基、4-ペンテニル基、ジメチルアリル基、1-ヘキセニル基、3-ヘキセニル基、5-ヘキセニル基、1-ヘプテニル基、3-ヘプテニル基、6-ヘプテニル基及び7-オクテニル基等が挙げられる。
Rbのアルコキシアルキル基としては、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、ペンチロキシメチル基、ヘキシロキシメチル基、ヘプチロキシメチル基、メトキシエチル基、エトキシエチル基、プロポキシエチル基、ブトキシエチル基、ペンチロキシエチル基、ヘキシロキシエチル基、メトキシプロピル基、エトキシプロピル基、プロポキシプロピル基、ブトキシプロピル基、メトキシブチル基、エトキシブチル基、プロポキシブチル基、メトキシペンチル基、エトキシペンチル基、メトキシヘキシル基及びメトキシヘプチル基等が挙げられる。
アルケニレン基としては、1,2-ビニレン基、1-フェニル-1,2-ビニレン基、5-ノルボルネン-2,3-ジイル基等が挙げられる。
本発明のいくつかの態様の感光性化合物は、上記Te原子含有基を有するオキシム骨格を有する感光性化合物であってもよい。オキシム骨格としては、下記式(7)で表されるものが挙げられ、オキシム骨格が直接又は連結基を介して上記Te原子含有基を有していれば、本発明はこれに限定されない。
Rd1及びRd2は、それぞれ独立して、置換基を有していても良い炭素原子数1~20の直鎖状、分岐鎖状若しくは環状のアルキル基、アリール基及びシアノ基等が好ましい。これらの基の水素原子の一部又は全部が置換基で置換されていてもよい。Rd1及びRd2のアルキル基及びアリール基は、上記式(1)のR1と同様のアルキル基及びアリール基が挙げられる。
Rd1及びRd2が有してもよい置換基としては、炭素原子数1~4のアルキル基又はアルコキシ基;炭素原子数5~20のアリール基;炭素原子数3~5の芳香族複素環基;ニトロ基;塩素原子及びフッ素原子等のハロゲン原子;等が挙げられる。また、上記R1の置換基と同様の置換基であってもよい。
Reが有してもよい置換基としては、炭素原子数1~4のアルキル基又はアルコキシ基;炭素原子数5~20のアリール基;炭素原子数3~5の芳香族複素環基;ニトロ基;塩素原子及びフッ素原子等のハロゲン原子;等が挙げられる。また、上記R1の置換基と同様の置換基であってもよい。
ウ素原子等が挙げられ、特にフッ素原子が好ましい。すなわち、ハロゲン化アルキル基は、フッ素化アルキル基であることが好ましい。
本発明のいくつかの態様の感光性化合物は、上記Te原子含有基を有していれば特に制限はなく、上記の他に、ホスホニウム塩、アンモニウム塩及びピリジニウム塩等のオニウム塩;グリオキシム化合物;ビススルホン酸化合物、β-ケトスルホン酸化合物及びジスルホン酸化合物等のスルホン化合物;スルホン酸エステル等の態様であってもよい。本発明のいくつかの態様の感光性化合物は、単独で又は2種類以上を組み合わせてレジスト組成物の成分として用いることができる。
本発明のいくつかの態様における感光性化合物は、光酸発生剤、光崩壊性塩基及び増感剤等として好適に用いられる。特に光酸発生剤及び光崩壊性塩基として用いられることが好ましい。
また上述したように、本発明のいくつかの態様における感光性化合物はポリマーであってもよい。感光性化合物がポリマーである場合、該ポリマーは感光性化合物として機能するユニットを含めばホモポリマーでもよく、また他のユニットを含むコポリマーであってもよい。コポリマーであるとき他のユニットとしては、酸反応性化合物として作用するもの、及び、ヒドロキシアリール基含有ユニット等が挙げられる。上記酸反応性化合物として作用するもの、及び、ヒドロキシアリール基含有ユニット等については、後述する。
本発明のひとつの態様における感光性化合物は、以下の方法により合成できる。
下記においては、上記式(2)においてYが硫黄原子であるスルホニウム塩の合成例を示す。まず、マグネシウムをTHFに添加して40~50℃に加熱し、これに、-R2a基と-R2b-Br基とを有するスルフィド化合物のテトラヒドロフラン(THF)溶液を滴下する。ここにR1基を有する有機テルル化合物のTHF溶液を50℃以下で滴下し、グリニャール反応により1~3時間反応させ、テルル含有スルフィドを得る。
テルル含有スルフィドをMCPBA等を用いてスルホキシドへ酸化後、グリニャール反応によりテルル含有スルホニウム塩化物塩を得る。その後、塩交換等により対応するX-を有するテルル含有スルホニウム塩化合物を得ることができる。
R2a及びR2cは、上記R1と同じ選択肢から選択される。R2bは上記R3と同じ選択肢から選択される。
まず、1-ブロモ-4-ヨードベンゼンとトリフルオロメタンスルホン酸とベンゼンとジクロロメタンとを混合する。ここにMCPBAジクロロメタン溶液を滴下して反応させ、4-ブロモフェニルフェニルヨードニウムトリフルオロメタンスルホン酸塩を得る。次いで、マグネシウムのTHF溶液に、4-ブロモフェニルフェニルヨードニウムトリフルオロメタンスルホン酸塩THF溶液を滴下する。ここにR1基を有する有機テルル化合物のTHF溶液を滴下し、グリニャール反応により反応させ、テルル含有ヨードニウムを得る。次いで塩交換等により対応するX-を有するテルル含有ヨードニウム塩化合物を得る
ことができる。
本発明のひとつの態様は、上記感光性化合物を含むレジスト組成物に関する。上記レジスト組成物は、上記感光性化合物を光酸発生剤、光崩壊性塩基及び増感剤のいずれかとして又は組み合わせてレジスト組成物の成分として用いることができる。
本発明のひとつの感光性化合物を光酸発生剤及び光崩壊性塩基として用い、オニウム塩構造を有する場合は、光崩壊性塩基のアニオンは、光酸発生剤のアニオンよりも酸強度が小さいもの適宜組み合わせて用いることが好ましい。より具体的には、光酸発生剤はpKaが-3以下であることが好ましい。そのようなアニオンとしては、フッ素置換スルホン酸等が挙げられる。
本発明のいくつかの態様において、pKaは、ACD labs(富士通(株)製)を用いて解析して得られた値である。
またレジスト組成物は、酸反応性化合物をさらに含むことが好ましい。
(その他の光酸発生剤)
本発明のいくつかの態様のレジスト組成物は、本発明のいくつかの態様の感光性化合物を光酸発生剤として用いる場合、その他の光酸発生剤(以下、「第二の光酸発生剤」ともいう)を含有していてもよい。そのような第二の光酸発生剤としては、通常のレジスト組成物に用いられるものであれば特に制限はなく、例えば、スルホニウム塩、ヨードニウム塩等のオニウム塩化合物、N-スルホニルオキシイミド化合物、オキシムスルホネート化合物、有機ハロゲン化合物、スルホニルジアゾメタン化合物等が挙げられる。これらは一種単独で又は二種以上を組み合わせて用いることができる。
スルホニウム塩としては、例えばWO2011/093139号公報に記載のものが挙げられる。
上記光酸発生剤がポリマーに結合する場合は、ポリマー主鎖を除いた質量基準とする。
本発明のひとつの態様のレジスト組成物はその他の光崩壊性塩基を含んでいても良い。
光崩壊性塩基は、上記のその他の光酸発生剤が有するカチオンと同様のものを用いることができる。そのとき光崩壊性塩基のアニオンは、上記光酸発生剤のアニオンよりも酸強度が小さいものを用いることが好ましい。
また、上記光崩壊性塩基のレジスト組成物中の含有量は光酸発生剤10質量に対し1~50質量部であることが好ましく、3~25質量部であることがより好ましい。上記範囲内で上記光崩壊性塩基をレジスト組成物中に含有させることで、感度、解像度及びパターン形成能に優れた特性を有することができる。
含有量の算出において、有機溶剤はレジスト組成物成分に含まないこととする。
また、上記光崩壊性塩基がポリマーに結合する場合は、ポリマー主鎖を除いた質量基準
とする。
なお、上記光崩壊性塩基は一種単独で又は二種以上を組み合わせて用いてもよい。
本発明のいくつかの態様のレジスト組成物は、酸反応性化合物を含有することが好ましい。
上記酸反応性化合物は、酸により脱保護する保護基を有する、酸により重合する、又は、酸により架橋することが好ましい。つまり、上記酸反応性化合物は、酸により脱保護する保護基を有する化合物、酸により重合する重合性基を有する化合物、及び、酸により架橋作用を有する架橋剤からなる群より選択される少なくともいずれかであることが好ましい。
酸で脱保護する保護基の具体例としては、エステル基、アセタール基、テトラヒドロピラニル基、カーボネート基、シロキシ基及びベンジロキシ基等が挙げられる。該保護基を有する化合物として、これら保護基がペンダントしたスチレン骨格、メタクリレート又はアクリレート骨格を有する化合物等が好適に用いられる。
酸により脱保護する保護基を有する化合物は、保護基含有低分子化合物であっても、保護基含有ポリマーであってもよい。本発明のいくつかの態様において、低分子化合物とは重量平均分子量が2000未満のものであり、ポリマーとは重量平均分子量が2000以上のものとする。
酸により重合する重合性基を有する化合物は、重合性低分子化合物であっても、重合性ポリマーであってもよい。
酸により架橋作用を有する化合物は、重合性低分子化合物であっても、重合性ポリマーであってもよい。
光酸発生剤が結合したユニット(V)を含有しても良い。
上記ポリマーは、例えば下記のようにして合成できる。上記各ユニット構成するモノマーをアゾビスイソブチロニトリル(AIBN)及びアゾビスイソ酪酸ジメチル等のラジカル重合開始剤を用いた公知のラジカル重合等により重合させることによって得ることができる。
なお、重合の際に、HS-CH2-CH2-CH2-C(CF3)2-OH等の連鎖移動剤を併用して用い、ポリマー末端に-C(CF3)2-OH基を導入してもよい。このように、アルキル基の水素原子の一部がフッ素原子で置換されたヒドロキシアルキル基が導入されたポリマーは、現像欠陥の低減やLERの低減に有効である。
本発明のひとつの態様のレジスト組成物には、上記成分以外に必要により任意成分として、通常のレジスト組成物で用いられる有機溶剤、酸拡散制御剤、界面活性剤、有機カルボン酸、溶解阻止剤、安定剤、色素及び増感剤等を組み合わせて含んでいてもよい。
ンアルコール、N-メチルピロリドン、N,N-ジメチルホルムアミド、γ-ブチロラクトン、N,N-ジメチルアセトアミド、プロピレンカーボネート、エチレンカーボネート等が好ましい。これらの有機溶剤は単独又は組み合わせて用いられる。
酸拡散制御剤としては、例えば、同一分子内に窒素原子を1個有する化合物、2個有する化合物、窒素原子を3個有する化合物、アミド基含有化合物、ウレア化合物、含窒素複素環化合物等が挙げられる。また、酸拡散制御剤として、露光により感光し弱酸を発生する本発明のひとつの態様の上記金属含有オニウム塩化合物以外の上記光崩壊性塩基を用いることもできる。具体的には、特許3577743号、特開2001-215689号、特開2001-166476号、特開2008-102383号、特開2010-243773号、特開2011-37835号及び特開2012-173505号に記載の化合
物が挙げられる。
酸拡散制御剤を含む場合その含有量は、上記酸反応性化合物100質量部に対して、0.01~20質量部であることが好ましく、0.03~15質量部であることがより好ましく、0.05~10質量部であることがさらに好ましい。上記含有量には、上記光崩壊性塩基は含まないものとする。
界面活性剤の含有量は、上記酸反応性化合物100質量部に対して0.0001~2質量部であることが好ましく、0.0005~1質量部であることがより好ましい。
有機カルボン酸の含有量は、上記酸反応性化合物100質量部に対して、0.01~10質量部が好ましく、より好ましくは0.01~5質量部、更により好ましくは0.01~3質量部である。
レジスト組成物成分は、上記有機溶剤に溶解し、固形分濃度として、1~40質量%で溶解することが好ましい。より好ましくは1~30質量%、更に好ましくは3~20質量%である。
本発明のいくつかの態様において、ポリマーの重量平均分子量及び分散度は、GPC測定によるポリスチレン換算値として定義される。
上記含フッ素はっ水ポリマーとしては、特に制限はないが液浸露光プロセスに通常用いられるものが挙げられ、上記ポリマーよりもフッ素原子含有率が大きい方が好ましい。それにより、レジスト組成物を用いてレジスト膜を形成する場合に、含フッ素はっ水ポリマーのはっ水性に起因して、レジスト膜表面に上記含フッ素はっ水ポリマーを偏在化させる
ことができる。
本発明のひとつの態様は、上記レジスト組成物を基板上に塗布する等してレジスト膜を形成する工程と、上記レジスト膜を露光する工程と、露光された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、を含むデバイスの製造方法である。
本発明のひとつの形態は、上記レジスト組成物を用いて、レジスト膜を形成する工程とパターンを形成する工程とを含み、個片化チップを得る前のパターンを有する基板の製造方法であってもよい。
本発明のひとつの態様において、露光する工程の露光に用いる活性エネルギー線としては、電子線(EB)又は極端紫外線(EUV)等が好ましく挙げられる。
上記レジスト組成物は、上記増感剤を含むか、対応する上記増感剤を増感ユニットとしてポリマーに含む場合、電子線又はEUV等の第1の露光後に、UV等で第2の露光を行うことも好ましい。
(合成例1)テルル含有スルフィドの合成
マグネシウム(0.64g)とTHFを添加した反応容器を40~50℃に加熱し、2-ブロモジベンゾチオフェン(5.79g)のTHF溶液を滴下し、グリニャール試薬を調製する。ここに、ジフェニルジテルリド(8.19g)のTHF溶液を滴下し、1~3時間反応後、一般的な後処理を行った。シリカゲルカラムクロマトグラフィー(n-ヘキサン100%)にて精製し、テルル含有スルフィド(3.14g)を得る。
合成例1で得たテルル含有スルフィド(1.16g)と、MCPBA(0.76g)、ジクロロメタン(5.78g)とを混合し、25℃で1~3時間反応させる。一般的な後処理を行った後、シリカゲルカラムクロマトグラフィー(メタノール/ジクロロメタン=20/80)にて精製し、テルル含有スルホキシド(0.60g)を得る。
合成例2で得たテルル含有スルホキシド(2.00g)と、1Mフェニルマグネシウムブロミド(6.00g)THF溶液と、トリメチルクロロシラン(1.60g)と、THF(36.0g)とを混合し、1時間撹拌する。通常の後処理後、シリカゲルカラムクロマトグラフィー(メタノール/ジクロロメタン=10/90)にて精製し、テルル含有スルホニウム塩化物塩(0.06g)を得る。
合成例3で得たテルル含有スルホニウム塩化物塩(1.62g)と、ノナフルオロブタンスルホン酸カリウム(1.21g)と、ジクロロメタン(16.2g)と、水(16.2g)とを混合し、1時間撹拌した。水で洗浄後、シリカゲルカラムクロマトグラフィー(メタノール/ジクロロメタン=5/95)にて精製し、テルル含有スルホニウム塩1(1.9g)を得る。
(合成例5)テルル含有スルホニウム塩2の合成
ノナフルオロブタンスルホン酸カリウムに代えてソジウム-4-(1-アダマンタンカルボニルオキシ)1,1,2-トリフルオロブタン-1-スルホナートとすること以外は合成例4と同様にして合成する。
(合成例6)テルル含有スルホニウム塩3の合成
ノナフルオロブタンスルホン酸カリウムに代えてソジウム-4-(3-ヒドロキシ-1-アダマンタンカルボニルオキシ)1,1,2-トリフルオロブタン-1-スルホナートとすること以外は合成例4と同様にして合成する。
(合成例7)テルル含有スルホニウム塩4の合成
合成例1において2-ブロモジベンゾチオフェンの代わりに4-ブロモフェニルフェニルスルフィドを用い、合成例4においてノナフルオロブタンスルホン酸カリウムの代わりにソジウム-4-(3-ヒドロキシ-1-アダマンタンカルボニルオキシ)1,1,2-トリフルオロブタン-1-スルホナートを用いた以外は合成例1~4と同様にして合成する。
(合成例8)ポリマー(A-1)の合成
各構成単位を誘導するモノマーを、ラジカル重合開始剤としてアゾビスイソブチロニトリル(AIBN)を用いた公知のラジカル重合等により重合させることによって、下記に示すポリマーA-1(重量平均分子量:約10000)を得る。下記式中、a=0.4、b=0.4、c=0.2であるが、本発明のいくつかの態様におけるポリマーのユニットのモノマー比は下記に限定されない。
(合成例9)ポリマー(A-2)の合成
各構成単位を誘導するモノマーを、ラジカル重合開始剤としてアゾビスイソブチロニトリル(AIBN)を用いた公知のラジカル重合等により重合させることによって、下記に示すポリマーA-2(重量平均分子量:約10000)を得る。下記式中、a=0.4、b=0.4、c=0.2であるが、本発明のいくつかの態様におけるポリマーのユニットのモノマー比は下記に限定されない。
(合成例10)ポリマー(A-3)の合成
各構成単位を誘導するモノマーを、ラジカル重合開始剤としてアゾビスイソブチロニトリル(AIBN)を用いた公知のラジカル重合等により重合させることによって、下記に示すポリマーA-3(重量平均分子量:約10000)を得る。下記式中、a=0.4、b=0.4、c=0.2であるが、本発明のいくつかの態様におけるポリマーのユニットのモノマー比は下記に限定されない。
ベース重合体としてのポリマー(A-1)、ポリマー(A-2)及びポリマー(A-3)のいずれか各100質量部と、光酸発生剤としてのテルル含有スルホニウム塩1を8質量部と、溶媒としてのプロピレングリコールモノメチルエーテルアセテート1800質量部とを混合し、その後PTFEフィルターでろ過して、レジスト組成物(H-1)溶液を調製した。レジスト組成物の詳細を表1に示す。
光酸発生剤としてテルル含有スルホニウム塩1に代えて上記で合成したテルル含有スルホニウム塩2~4のいずれかを表1に示す配合量で用いる以外は実施例1と同様にして、レジスト組成物(H-2)~(H-12)を得る。
[比較例1~12]
なお、上記光酸発生剤(B-1)~(B-4)を下記に示す。
各レジスト組成物をシリコンウェハ上にスピンコータにより回転塗布した後、ホットプレート上で110℃で60秒間プレベークし、膜厚150nmの塗布膜を得た。90nmのラインパターンが得られるようにマスクを用い、ArFエキシマレーザにより露光し、次いで110℃で90秒間ポストベークを行う。その後、2.38質量%のテトラメチルアンモニウムヒドロキシド水溶液を用いて60秒間現像を行い、その後30秒間純水でリンスしてパターン形成された基板を得る。
このときの解像性、焦点深度及びラインエッジラフネスを比較例1の値を基準とし、基準と比べたときの実施例1~12及び比較例2~12の感度、解像性、焦点深度及びラインエッジラフネスの各性能を下記を指標として評価する。なお、レジストパターンの測長には走査型電子顕微鏡を用いる。
○:比較例1に対して10%以上の向上が見られた場合。
△:比較例1に対して10%未満、5%以上の向上の場合。
×:比較例1に対して5%未満の向上の場合。
90nmのラインパターンを再現する最小露光量により解像できるラインパターンの幅(nm)、即ち、限界解像力を示す。解像性は、数値が小さいほど良好である。
(焦点深度)
焦点の位置を上下に移動させて、マスクにおける90nmパターンを再現する最小露光量で露光し、ポストベーク(PEB)及び現像を行ったときに、90nmのラインパターンを再現できる許容可能な焦点の範囲を示す。焦点の範囲が大きいほど焦点深度の変化に対するパターン寸法変化が小さく良好である。
90nmのラインパターンを再現する最小露光量により得られた90nmのラインパターンの長手方向のエッジ2.5μmの範囲について、エッジがあるべき基準線からの距離を50ポイント測定し標準偏差(σ)を求め、その3倍値(3σ)をLERとして算出した。値が小さいほどラフネスが小さく均一なパターンエッジが得られ良好な性能である。
感度評価
<レジスト組成物の調製>
ベース重合体としてのポリマー(A-1)100質量部と、光酸発生剤として下記式(B-5)に示すトリフルオロメタンスルホナート=トリフェニルスルホニウムと、テルル含有スルホニウム塩1と、溶媒としてのプロピレングリコールモノメチルエーテルアセテート3000質量部とを混合し、その後PTFEフィルターでろ過して、レジスト組成物(H-25)溶液を調製した。レジスト組成物の詳細を表3に示す。
光酸発生剤トリフルオロメタンスルホナート=トリフェニルスルホニウム、及びテルル含有スルホニウム塩1を表3に示す配合量で用いる以外は実施例13と同様にして、レジスト組成物(H-26)を得る。
各レジスト組成物をシリコンウェハ上にスピンコータにより回転塗布した後、ホットプレート上で110℃で60秒間プレベークし、膜厚50nmの塗布膜を得る。EUVにより露光し、次いで110℃で60秒間ポストベークを行った。その後、2.38質量%のテトラメチルアンモニウムヒドロキシド水溶液を用いて60秒間現像を行い、その後30秒間純水でリンスしてパターン形成された基板を得る。
このとき、形成したレジスト膜の残膜が0となる露光量を感度として評価する。
また、実施例13、14及び比較例13に示すように、感度評価において、光酸発生剤に上記テルル含有スルホニウム塩を適量混合することで感度増加が得られることがわかる。なお、光酸発生剤として上記式(B-5)に示す光酸発生剤に代えて、上記光酸発生剤(B-1)~(B-4)のいずれかを上記テルル含有スルホニウム塩と併用した場合も実施例13及び14と同様の結果が得られる。
以上の結果から、本発明のひとつの態様における感光性化合物は、リソグラフィにおける感度、解像性、焦点深度に優れ、且つ、微細パターンにおけるLERを低減できる効果を有することがわかる。
Claims (10)
- 2価のTe原子を含有する感光性化合物。
- オニウム塩骨格、ジアゾメタン骨格、イミド骨格及びオキシム骨格から選択されるいずれかの骨格を有し、
前記骨格が、下記式(1)で表されるTe原子含有基を有する請求項1に記載の感光性化合物。
前記炭化水素基及び前記アリール基が有する水素原子の一部又は全部が置換基で置換されていてもよく、
前記炭化水素基がメチレン基を有するとき、少なくとも1つのメチレン基に代えて2価のヘテロ原子含有基を含んでいても良く、
前記アリール基は、環構造中に少なくとも1つの炭素原子に代えてヘテロ原子を含んでいても良く、
*は、前記骨格との結合部位を示す。) - 請求項1~3のいずれか一項に記載の感光性化合物を含む光酸発生剤。
- 請求項1~3のいずれか一項に記載の感光性化合物又は請求項4に記載の光酸発生剤を含有するレジスト組成物。
- 酸反応性化合物をさらに含有する請求項5に記載のレジスト組成物。
- 第二の光酸発生剤をさらに含有する請求項5又は6に記載のレジスト組成物。
- 前記酸反応性化合物が、酸により脱保護する保護基を有する化合物、酸により重合する重合性基を有する化合物、及び、酸により架橋作用を有する架橋剤からなる群より選択される少なくともいずれかである請求項6又は7に記載のレジスト組成物。
- 請求項5~8のいずれか一項に記載のレジスト組成物を用いて基板上にレジスト膜を形成する工程と、
前記レジスト膜を露光する工程と、
露光された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、を含むデバイスの製造方法。 - 前記レジスト膜の露光が、電子線又は極端紫外線を用いて行われる請求項9に記載の製造方法。
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WO2019066000A1 (ja) * | 2017-09-29 | 2019-04-04 | 学校法人関西大学 | リソグラフィー用組成物、パターン形成方法、及び化合物 |
JP2022003406A (ja) * | 2017-11-30 | 2022-01-11 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | 塩およびこれを含むフォトレジスト |
US11932713B2 (en) * | 2017-12-31 | 2024-03-19 | Rohm And Haas Electronic Materials Llc | Monomers, polymers and lithographic compositions comprising same |
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TWI683801B (zh) | 2017-11-30 | 2020-02-01 | 美商羅門哈斯電子材料有限公司 | 兩性離子化合物及包括其之光阻 |
JP7038211B2 (ja) * | 2018-06-29 | 2022-03-17 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及びフォトマスク |
JP2020029451A (ja) * | 2018-08-17 | 2020-02-27 | 住友化学株式会社 | 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
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