WO2008038448A1 - Composition de résist de type négatif pour un faisceau d'électrons, et procédé de formation d'un motif de résist - Google Patents

Composition de résist de type négatif pour un faisceau d'électrons, et procédé de formation d'un motif de résist Download PDF

Info

Publication number
WO2008038448A1
WO2008038448A1 PCT/JP2007/064002 JP2007064002W WO2008038448A1 WO 2008038448 A1 WO2008038448 A1 WO 2008038448A1 JP 2007064002 W JP2007064002 W JP 2007064002W WO 2008038448 A1 WO2008038448 A1 WO 2008038448A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
electron beam
acid
resist composition
alkyl group
Prior art date
Application number
PCT/JP2007/064002
Other languages
English (en)
Japanese (ja)
Inventor
Kiyoshi Ishikawa
Yoshinori Sakamoto
Original Assignee
Tokyo Ohka Kogyo Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Ohka Kogyo Co., Ltd. filed Critical Tokyo Ohka Kogyo Co., Ltd.
Publication of WO2008038448A1 publication Critical patent/WO2008038448A1/fr

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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

Definitions

  • the present invention relates to a negative resist composition for electron beam and a resist pattern forming method.
  • a resist film made of a resist material is formed on a substrate, for example, and a light or electron beam is passed through a mask in which a predetermined pattern is formed on the resist film.
  • a step of forming a resist pattern having a predetermined shape on the resist film is performed by performing selective exposure with radiation such as, and developing the resist.
  • Resist materials that change their properties so that the exposed part dissolves in the developer are positive, resists that do not dissolve in the developer are negative, and resist materials that change their characteristics are negative.
  • the wavelength of an exposure light source is generally shortened.
  • the power used in the past typically ultraviolet rays such as g-line and i-line, is now in the process of mass production of semiconductor devices using KrF excimer laser and ArF excimer laser.
  • excimer lasers have shorter wavelength excimer lasers, electron beams, EUV (n-rays), EUV (n-rays, EUV).
  • Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
  • a chemically amplified resist containing a base resin whose alkali solubility is changed by the action of an acid and an acid generator that generates an acid upon exposure is used.
  • a positive chemically amplified resist contains an acid dissociable, dissolution inhibiting group as a base resin, contains a resin component that increases alkali solubility by the action of an acid, and an acid generator. Occasionally, when an acid is generated from the acid generator by exposure, the exposed area becomes alkali-soluble.
  • a negative chemically amplified resist contains, for example, a resin component having a carboxy group, a crosslinking agent having an alcoholic hydroxyl group, and an acid generator, and an acid generated from the acid generator when forming a resist pattern.
  • the carboxy group of the resin component and the alcoholic hydroxyl group of the cross-linking agent react to change the resin component from alkali-soluble to insoluble.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-241385
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a novel negative resist composition for electron beams and a resist pattern forming method using the negative resist composition for electron beams.
  • the present invention employs the following configuration.
  • the first aspect of the present invention is a condensation of a hydrolyzate of an alkoxysilane compound represented by the following general formula (I) and an alkoxysilane compound represented by the following general formula (I): At least one compound (A) selected from the group consisting of A negative resist composition for an electron beam comprising a crude agent (B).
  • R 1 is a hydrogen atom or a monovalent organic group
  • R 2 is a monovalent organic group
  • n is an integer of 1 to 3.
  • the second aspect of the present invention includes a step of forming a resist film on a substrate using the negative resist composition for an electron beam according to the first aspect (aspect), the resist film And a resist pattern forming method including a step of developing the resist film to form a resist pattern.
  • an “organic group” is a group containing a carbon atom, and is an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine Atoms, chlorine atoms, etc.))).
  • alkyl group includes straight-chain, branched-chain and cyclic monovalent saturated hydrocarbon groups unless otherwise specified.
  • “Lower alkyl group” means an alkyl group having from 5 to 5 carbon atoms.
  • Exposure means irradiation with an electron beam unless otherwise specified.
  • the present invention can provide a novel negative resist composition for electron beam and a resist pattern forming method using the negative resist composition for electron beam.
  • the negative resist composition for electron beam of the present invention comprises a hydrolyzate of an alkoxysilane compound represented by the general formula (I) and a condensate of an alkoxysilane compound represented by the following general formula (I).
  • At least one compound selected from the group (A) hereinafter referred to as component (A)
  • a nonionic acid generator (B) hereinafter referred to as component (B)
  • the component (A) is a hydrolyzate and / or condensate of an alkoxysilane compound represented by the general formula (I).
  • the alkoxy group becomes a hydroxyl group by hydrolysis to form an alcohol. Thereafter, two molecules of the alcohol are condensed to form a Si-0-Si network, whereby the component (A) is obtained.
  • R 1 is a hydrogen atom or a monovalent organic group
  • R 2 is a monovalent organic group
  • examples of the monovalent organic group include an alkyl group, a aryleno group, an aryleno group, and a glycidinole group. Of these, alkyl groups and aryl groups are preferred.
  • the force, the alkyl group, and the aryl group may have a substituent.
  • substituent As the substituent,
  • “having a substituent” means, for example, that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
  • Preferred examples of the alkyl group include those having! To 5 carbon atoms (lower alkyl group), such as a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the alkyl group may be linear or branched, as described above, for example, when a hydrogen atom is substituted with a fluorine atom or the like.
  • aryl group those having 6 to 20 carbon atoms are preferred, and examples thereof include a phenyl group and a naphthyl group.
  • n is an integer of 1 to 3.
  • alkoxysilane compound represented by the general formula (I) include the following.
  • trialkoxysilane compounds such as trimethoxysilane compounds, triethoxysilane compounds, tripropoxysilane compounds (when R 1 is a hydrogen atom);
  • Monomethyltrimethoxysilane compound monomethyltriethoxysilane compound, monomethyltripropoxysilane compound, monoethyltrimethoxysilane compound, monoethyltriethoxy
  • Monoalkyltrialkoxysilane compounds such as silane compounds, monoethyl tripropoxysilane compounds, monopropyltrimethoxysilane compounds, monopropyltriethoxysilane compounds;
  • Examples thereof include monophenyltrialkoxysilane compounds such as monophenyltrimethoxysilane compounds and monophenyltriethoxysilane compounds.
  • dialkoxysilane compounds such as dimethoxysilane compounds, methoxysilane compounds, dipropoxysilane compounds (when R 1 is a hydrogen atom);
  • diphenyldialkoxysilane compounds such as dialkyldiphenyldimethoxysilane compounds such as dipropyldipropoxysilane compounds and diphenyljetoxysilane compounds.
  • alkoxysilane compounds such as methoxysilane compounds, ethoxysilane compounds, and propoxysilane compounds (when R 1 is a hydrogen atom);
  • Trimethylmethoxysilane compound such as a compound;
  • triphenylalkoxysilane compounds such as triphenylmethoxysilane compounds and triphenylethoxysilane compounds.
  • trialkoxysilane compounds such as trimethoxysilane compounds, triethoxysilane compounds, tripropoxysilane compounds (when R 1 is a hydrogen atom); monomethylenotrimethoxysilane compounds, monomethyltriethoxysilane compounds, Particularly preferred is a trialkoxysilane compound (when R 1 is a hydrogen atom), which is preferably a monomethyltrialkoxysilane compound such as a monomethyltripropoxysilane compound. Of these, triethoxysilane compounds are the most preferred.
  • the alkoxysilane compound represented by the general formula (I) may be used alone or in combination of two or more. .
  • the negative resist composition for electron beam of the present invention contains a condensate of an alkoxysilane compound represented by the general formula (I), the mass average molecular weight of the condensate
  • Mw polystyrene conversion standard by gel permeation chromatography
  • Mw polystyrene conversion standard by gel permeation chromatography
  • the condensate of the alkoxysilane compound represented by the general formula (I) is obtained by reacting an alkoxysilane compound as a polymerization monomer in an organic solvent in the presence of an acid catalyst.
  • an alkoxysilane compound represented by the general formula (I)
  • the solution containing the condensate of the alkoxysilane compound obtained here is referred to as “silan-based coating forming coating solution”.
  • the alkoxysilane compound used as the polymerization monomer can be used alone or in combination of two or more.
  • an alkylene glycol dialkyl ether is preferably used because the storage stability (for example, the effect of preventing gelation) of the coating solution for forming a silane-based film is improved.
  • alkylene glycol dialkyl ethers include, for example, ethylene glycol noremethino enoate, ethylene glycol eno chineno ethenore, ethylene glycono dioleno pineolate, ethylene glycol enores butyl enoate, diethylene gluconoresin mino enoate, diethylene glycol.
  • organic solvents may be used alone or in combination of two or more thereof.
  • the amount used is 10 to 30 times the amount of one mole of the alkoxysilane compound.
  • the degree of hydrolysis of the alkoxysilane compound which is a precondition for condensation, is a force that can be adjusted by the amount of water to be added.
  • the total moles of the alkoxysilane compound represented by the above general formula (I) It is preferable to add at a ratio of 1 to 10-fold moles relative to the number, more preferably 1.5 to 8-fold moles.
  • the amount of water added is at least 1 mol, the degree of hydrolysis increases, and the condensation reactivity between alkoxysilane compounds (the above alcohols) improves.
  • the amount is 10 times or less, gelation is suppressed, and the storage stability of the coating solution for forming a silane-based film is improved.
  • the acid catalyst used in the condensation of the alkoxysilane compound represented by the general formula (I) is not particularly limited, and any of conventionally used organic acids and inorganic acids can be used. Can also be used.
  • organic acid examples include organic carboxylic acids such as acetic acid, propionic acid, and butyric acid.
  • examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like.
  • the acid catalyst may be added directly to the mixture of the alkoxysilane compound and water, or may be added as an acidic aqueous solution together with water to be added to the alkoxysilane compound.
  • the hydrolysis reaction is usually completed in about 5 to about 100 hours.
  • an acid catalyst aqueous solution is dropped into an organic solvent containing one or more alkoxysilane compounds represented by the above general formula (I) to cause a short reaction. It is also possible to complete the reaction in time.
  • the hydrolyzed alkoxysilane compound subsequently undergoes a condensation reaction. As a result, a Si_O_Si network is formed and component (A) is obtained.
  • the component (A) contains a hydrolyzate of an alkoxysilane compound together with a condensate of the alkoxysilane compound.
  • the component (A) is suitably used, for example, in the state of the above-mentioned coating solution for forming a silane-based film.
  • This coating solution for forming a silane-based film is obtained by concentrating a solution obtained by hydrolyzing and condensing an alkoxysilane compound represented by the above general formula (I) or by using an organic solvent (preferably And the like, for example, by diluting with the above-mentioned alkylene glycol dialkyl ether, etc.).
  • Such solid content concentration can be measured, for example, by a weight drying method.
  • the mass (W1) of the collected coating solution for forming a silane-based film is measured, dried at 500 ° C for 1 hour, and the mass after drying (W2) is obtained. This is a method for calculating the partial concentration.
  • the concentration of the coating solution for forming the silane film is approximated as the SiO equivalent concentration of component (A).
  • the SiO equivalent concentration is based on the solid content concentration (% by mass) calculated by the above formula.
  • the SiO equivalent concentration of the coating solution for forming a silane-based film depends on the purpose of use.
  • the component (B) is a nonionic acid generator.
  • This component (B) is a compound that generates an acid in response to an electron beam.
  • a resist pattern By containing the component (B), a resist pattern can be obtained by development. This is presumably because acid is generated by electron beam irradiation, and the formation of the Si-O-Si network between components (A) is promoted.
  • the film stability (PCD: post coating delay) after coating film formation is improved, and the solubility in an alkali developer is improved.
  • the component (B) has a small change in solubility in a developer (particularly an alkali developer) and is stable.
  • the component (B) is not particularly limited, and those conventionally proposed as acid generators for chemically amplified resists can be used.
  • nonionic acid generators include oxime sulfonate acid generators; diazomethane acid generators such as bisalkyl or bisarylsulfonyldiazomethanes and poly (bissulfonyl) diazomethanes.
  • Dalioxime acid generator bissulfonate acid generator, / 3-ketosulfone acid generator, disulfone acid generator, nitrobenzenosulfonate acid generator, sulfonate ester acid generator, N-hydroxy
  • imide compounds such as sulfonic acid ester acid generators and imino sulfonate acid generators are known.
  • the oxime sulfonate acid generator is a compound (B-1) having at least one group represented by the following general formula (II), and is an electron It has the property of generating acid upon irradiation with rays.
  • B_l Such an oxime sulfonate-based acid generator (B_l) is widely used for chemically amplified resist compositions, and can be arbitrarily selected and used.
  • R 31 and R 32 each independently represents an organic group.
  • the organic group for R 31 is preferably a linear, branched or cyclic alkyl group or aryl group. These alkyl groups and aryl groups may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a fluorine atom, a linear, branched or cyclic alkyl group having 6 to 6 carbon atoms.
  • carbon number 1 to 20 is preferable. Carbon number 10 is more preferable. Carbon number 1 to 8 is more preferable. Carbon number 1 to 6 is particularly preferable. Is 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 the hydrogen atoms are halogen atoms.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • fluorine atoms are preferred. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
  • the aryl group preferably has 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • aryl group a partially or completely halogenated aryl group is particularly preferable.
  • a partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is replaced by a halogen atom, and a fully halogenated aryl group means that all hydrogen atoms are halogen atoms.
  • R 31 in particular, an alkyl group having 1 to 4 carbon atoms having no substituent, or 1 carbon atom
  • organic group for R 32 a linear, branched or cyclic alkyl group, aryl group or cyan group is preferable.
  • alkyl group and aryleno group for R 32 the same alkyl groups and aryl groups as those described above for R 31 can be used.
  • R 32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.
  • More preferable examples of the oxime sulfonate acid generator (B-1) include compounds represented by the following general formula (B-2) or (B-3).
  • R 33 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group
  • R 34 is an aryl group
  • R 35 is an alkyl having no substituent. Group or a halogenated alkyl group.
  • alkyl or halogenated alkyl group which includes no substituent R 33 is 1 to carbon atoms: preferably from 10 tool 1 to 8 carbon atoms More preferred C 1-6 is most preferred.
  • R 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group for R 33 preferably has 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. .
  • the aryl group of R 34 includes a hydrogen atom from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, or a phenanthryl group. And a heteroaryl group in which a part of the carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom. Among these, a fluorenyl group is preferable.
  • the aryl group of R 34 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group.
  • the alkyl group or halogenated alkyl group in the substituent preferably has 1 to 4 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the halogenated alkyl group is preferably a fluorinated alkyl group.
  • the alkyl group or halogenialkyl group having no substituent of R 35 has a carbon number of:!
  • R 35 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group, and most preferably a partially or fully fluorinated alkyl group.
  • the fluorinated alkyl group in R 35 preferably has a hydrogen atom of the alkyl group of 50% or more fluorinated, more preferably 70% or more, and still more preferably 90% or more. This is preferable because the strength of the generated acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.
  • the alkyl group or halogenated alkyl group having no R db substituent does not have the R 33 substituent in the general formula (B-2). Examples thereof are the same as those for the alkyl group or the halogenated alkyl group.
  • Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups in which 1 or 2 hydrogen atoms have been further removed from the 4 aryl group in the general formula (B — 2).
  • the alkyl group or halogenated alkyl group having a substituent of R 38 is the same as the alkyl group or halogenated alkyl group having no substituent of R 35 in the general formula (B — 2). Things.
  • P ′ ′ is preferably 2.
  • oxime sulfonate acid generator (B_l) include bis (p_toluenesulfonyloxymino) monobenzyl cyanide, bis- (p-chlorobenzenebenzenesulfonyloxy).
  • an oxime sulfonate-based acid generator disclosed in JP-A-9 208554 (paragraphs [0012] to [0014] [Chemical Formula 18] to [Chemical Formula 19]), International Publication No. 04/074242
  • An oxime sulfonate acid generator disclosed in (Examples 40 to 65 on pages 65 to 85) can also be suitably used.
  • diazomethane acid generator examples include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfoninole) diazomethane, bis (xylenesulfoninore) diazomethane,
  • Diazomethane bis (n-butylsulfonino) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfoninole) diazomethane, bis (n-propylsulfonino) diazomethane, bis (isopropylsulfoninole) diazomethane, bis (Tert-Butylsulfonyl) diazomethane, bis ( n- amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsnorhoninole) diazomethane, 1-cyclohexylsulfonyl _ 1 _ (tert-butylsulfonino) diazomethane, 1-cyclo
  • Examples of the darioxime acid generator include, for example, bis-O- (p-toluenesulfonyl) -a -dimethyldaridioxime, bis-l-O- (p-toluenesulfonyl) ⁇ - diphenordridoxime, bis-l-( ⁇ Toluenesulfonyl) ⁇ -dicyclohexylglyoxime, bis-one ⁇ — ( ⁇ Toluenesulfonyl) 2, 3 Pentanedione glyoxime, bis ⁇ ( ⁇ Toluenesulfonyl) one 2 Methyl 3, 4-pentanedione glyoxime, bis-one ⁇ — ( ⁇ -butanesulfonyl) ⁇ -dimethyl darilioxime, bis ⁇ — ( ⁇ —butanesulfonyl) monodiphenyl daroxime, bis _ ( ⁇ -butanesulfony
  • Examples of the bissulfone-based acid generator include bisnaphthylsulfonylmethane, bistrinoleolomethinolesnorenoninomethane, bismethinoresnorenoninomethane, bisethinoresnolenomethane, bispropylsulfonyl.
  • Examples include methane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane.
  • Examples of the ⁇ -ketosulfone-based acid generator include 2-cyclohexylcarbonyl-2- ( ⁇ toluenesulfoninole) propane, 2-isopropylcarbonyl 2- ( ⁇ toluenesulfonyl) propane, and the like.
  • Examples of the disulfone-based acid generator include diphenyldisulfone derivatives, dihexyldisulfone derivatives, and the like.
  • nitrobenzyl sulfonate acid generator examples include ⁇ toluenesulfonic acid 2,6 dinitrobenzyl, ⁇ toluenesulfonic acid 2,4 dinitrobenzyl, and the like.
  • Examples of the sulfonic acid ester-based acid generator include 1, 2, 3-tris (methanesulfonyloxy) benzene, 1, 2, 3-tris (trifluoromethanesulfonyloxy) benzene, 1, 2, And 3-tris ( ⁇ -toluenesulfonyloxy) benzene.
  • Examples of the sulfonic acid ester-based acid generator for the ⁇ -hydroxyimide compound include ⁇ -hydroxysuccinimide methanesulfonate, ⁇ -hydroxysuccinimide trifluoromethanesulfonate, and ⁇ -hydroxysuccinimide ethanesulfonic acid.
  • esters N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p Toluene Sulfonic acid ester, N hydroxysuccinimide p Methoxybenzene sulphonic acid ester, N-hydroxysuccinimide 2 _Ethane sulfonic acid ester, N-hydroxysuccinimide benzene sulphonic acid ester, N-hydroxysuccinimide 2, 4, 6 _Trimethyl Benzenesulfonic acid ester, N —hydroxysuccinimide 1-naphthalenesulfonic acid ester, N hydroxysuccinimide 2 _Naphthalenesulfonic acid Steal, N-hydroxy-1-phenyl succ
  • one type of these acid generators may be used alone, or two or more types may be used in combination.
  • an oxime sulfonate acid generator (B-1) having a group represented by the general formula (II) is included as the component (B). Is most preferred.
  • the content of the component (B) in the electron beam negative resist composition of the present invention is, for example, 3 to 15 mass with respect to the SiO equivalent concentration of the component (A) in the silane-based coating forming coating solution. %, Preferably 5 to 10% by mass.
  • the negative resist composition for electron beam of the present invention further contains a miscible component if desired.
  • a contrast enhancer for example, a contrast enhancer, an organic solvent, and the like can be appropriately added and contained.
  • the negative resist composition for electron beam of the present invention may contain a contrast enhancer.
  • a contrast enhancer controls the solubility of a resist film (cured film) formed in response to light (electron beam), Z, or heat in the developer, thereby improving the contrast due to the unevenness of the resist film after development.
  • the component to enhance is shown.
  • the contrast enhancer is not particularly limited as long as it has the above-described functions, and is not limited to any known compound depending on the composition of the negative resist composition for electron beams, the type of developer, and the like. It is possible to appropriately select from the force.
  • strong contrast enhancer examples include photoacid generators other than the component (B), thermal acid generators, photobase generators, thermal base generators and the like.
  • the photoacid generator is not particularly limited as long as it is other than the component (B).
  • an onium salt can be used.
  • the onium salt include tetramethyl ammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, and nonafluoro Tetraphenylammonium lobutanesulfonate, tetramethylammonium p-toluenesulfonate, diphenylsulfonyl trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl), p-toluene Diphenyl fluoride toluene, p-toluenesulfonic acid (p_tert_butoxyphenole), phenylsulfonyl trifluorenylsulfonic acid triphenylsulfonium, trifluoromethanesulfonic
  • the thermal acid generator is a compound that generates an acid in response to heat.
  • the thermal acid generator is not particularly limited, and examples thereof include 2, 4, 4, 6-tetrabromocyclohexagenone, benzoin tosylate, 2-nitrobenzene ditosylate, and other alkyl esters of organic sulfonic acid.
  • a conventional thermal acid generator such as a composition containing at least one of these thermal acid generators can be used.
  • the photobase generator is a compound that generates a base in response to light (electron beam).
  • photobase generators include, but are not limited to, photoactive power rubamates such as triphenyl methanol, benzyl carbamate and benzoin carbamate; ⁇ _Strong rubamoyloxime, aromatics, honamide, alpha-latatatam, amides such as N- (2-allyl) amide, and other amides; oxime esters, monoaminoacetophenones, cobalt complexes Can raise 'S' ability.
  • photoactive power rubamates such as triphenyl methanol, benzyl carbamate and benzoin carbamate
  • ⁇ _Strong rubamoyloxime aromatics, honamide, alpha-latatatam
  • amides such as N- (2-allyl) amide, and other amides
  • oxime esters monoaminoacetophenones, cobalt complexes Can raise 'S' ability.
  • the thermal base generator is a compound that generates a base in response to heat.
  • the thermal base generator is not particularly limited, but examples thereof include 1_methyl_1_ (4-biphenylyl) ethylcarbamate, 1,1-dimethyl_2-cyanethylcarbamate, and the like.
  • the compounding amount of the contrast enhancer in the electron beam negative resist composition of the present invention is 0.:! With respect to the SiO equivalent concentration of the component (i) in the silane-based coating forming coating solution.
  • the blending amount of the contrast enhancer By setting the blending amount of the contrast enhancer to 0.1% by mass or more, the effect of the contrast enhancer can be sufficiently obtained, and the resist pattern formed after processing with the developer has sufficient contrast. be able to.
  • the retention stability of the negative resist composition for electron beams can be improved by setting the blending amount of the contrast enhancer to 30% by mass or less. In addition to the improvement, it is possible to prevent a decrease in the amount of film reduction in the exposed area during development and to prevent a decrease in contrast.
  • the negative resist composition for an electron beam of the present invention contains an organic solvent (hereinafter sometimes referred to as (S) component) for the purpose of improving coating properties and film thickness uniformity. Is preferred
  • monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, 3-methoxy_3_methyl_1-butanol, 3-methoxy-1-butanol; methyl_3-methoxy Alkylcarboxylic acid esters such as propionate and ethyl _3_ethoxypropionate; polyhydric alcohols such as ethylene glycol, diethylene glycol and propylene glycol; ethylene glycol monomethyl ethereol, ethylene glycol monoethanolo ethere , Ethylene glycol monopropylene etherate, ethylene glycol / lemonobutinoate ethere, propylene glycol monomonomethylene ether, propylene glycol monoethyl ether, propylene glycol monopropylene Polyhydric alcohol derivatives such as ether, propylene glycol monobutyl ether, ethylene glyco
  • the component (S) may be used alone or in combination of two or more.
  • the amount of the component (S) is not particularly limited, but it is preferable that the concentration of the component (solid content) other than the component (S) is 5 to: 100% by mass 20 to 50% by mass Is more preferable. By making it in the above range, the coating property to the substrate or the like can be improved.
  • additives such as other resins, surface active agents, adhesion assistants and the like can be blended within a range not impairing the effects of the present invention.
  • the additive can be appropriately selected depending on the function desired to be imparted.
  • a surfactant When a surfactant is added, the coating property of the negative resist composition for electron beams is improved, and the flatness of the resulting resist film is also improved.
  • surfactants include BM-1000 (trade name; manufactured by BM Chemie); Megafax F142D, F172, F173, and F183 (above, trade names; Dainippon Ink Chemical Co., Ltd.) ); Fluorad FC-135, FC-170C, FC-430, and FC_431 (Product name: Sumitomo 3EM); Surflon S_112, S_113, S_ 131, S_141, and S_145 (trade name; manufactured by Asahi Glass Co., Ltd.); S H-28PA, SH—190, SH—193, SZ—6032, SF—8428, DC—57, and Fluorosurfactants such as D C — 190 (trade name; manufactured by Toray Silicone Co., Ltd.) can be used.
  • the ratio in the case of using the surfactant in the negative resist composition for electron beam is usually preferably 5 parts by mass or less with respect to 100 parts by mass of components (solid content) other than the surfactant. More preferably, it is 0.01 to 2 parts by mass.
  • an adhesion assistant preferably, a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group is used.
  • the functional silane coupling agent include, for example, trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ -isocyanatepropyltriethoxysilane. ⁇ -glycidoxypropyl trimethoxysilane, mono (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
  • the ratio is 100 parts by mass or less of components other than the adhesion assistant (solid content), usually 20 parts by mass or less. More preferably 0.05 to 10 parts by mass, particularly preferably 1 to 10 parts by mass.
  • the resist pattern forming method of the present invention includes a step of forming a resist film on a substrate using the negative resist composition for electron beams of the present invention, a step of exposing the resist film, and developing the resist film. And a step of forming a resist pattern.
  • a powerful resist pattern forming method can be performed, for example, as follows. That is, first, a negative resist composition for electron beam is applied onto a substrate such as silicon wafer by a spinner (spin coating method) or the like, and pre-beta (post-applied) is performed at a temperature of 100 to 250 ° C. Beta (PAB)) is applied for 20 to 200 seconds, preferably 60 to 150 seconds, and an electron beam is selectively exposed through a desired mask pattern by, for example, an electron beam drawing machine.
  • PAB photo-beta
  • PEB post-exposure heating
  • PEB post-exposure heating
  • 20 to 200 seconds preferably 60 to 150 seconds under a temperature condition of 100 to 250 ° C.
  • PEB post-exposure heating
  • an alkali developer for example, an aqueous solution of 5 to 20% by mass of tetramethylammonium hydroxide.
  • An organic or inorganic antireflection film may be provided between the substrate and the coating layer of the resist composition.
  • a novel negative resist composition for electron beam and a resist pattern forming method using the negative resist composition for electron beam can be provided.
  • a resist film formed by applying a negative resist composition for electron beam on a substrate and pre-beta (PAB), Excellent film stability (PCD) after coating and good solubility in alkaline developer.
  • PAB pre-beta
  • PCD Excellent film stability
  • the resist pattern obtained using the negative resist composition for electron beams of the present invention can be suitably used as a mold (original) for imprint lithography.
  • a coating solution for forming a silane-based film having a concentration of 10% by mass and an ethanol concentration of 1% by mass was produced.
  • the oxime sulfonate acid generator represented by the following chemical formula is used in an amount of 0.7 parts by mass (in the coating liquid). 7 mass%) of the triethoxysilane condensate in terms of SiO concentration
  • a negative resist composition was prepared.
  • the negative resist composition for electron beam obtained in Example 1 obtained above was applied on an 8-inch silicon wafer by spin coating, and then baked (PAB) at 180 ° C. for 120 seconds to form a film. A 300 nm thick resist film (cured film) was formed.
  • the resist film (cured film) obtained above was drawn with an electron beam drawing machine (Hitachi HL-1800D, 70 kV high-speed voltage), and drawn with an electron beam, and then the temperature was changed to 23 ° C This was developed with a 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, washed with water, and then shaken and dried.
  • TMAH tetramethylammonium hydroxide
  • a resist film ( A cured film) was formed.
  • each resist film was subjected to the conditions shown in Tables:! To 3; that is, following the formation of the resist film (Table 1), and after 15 days (Table 2), the resist film was immersed in water for 10 seconds. After that (Table 3), the film was developed with a 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C. for 60 seconds, washed with water, and dried by shaking. The PCD was evaluated by measuring the film thickness at this time. The results are shown in Tables!
  • Comparative Example 1 which is different from the present invention, a residue was recognized by development processing after 15 days (Table 2), and a residual film was observed by development processing after immersion for 10 seconds in water. (Table 3)
  • a resist film formed by applying a negative resist composition for electron beam on a substrate and pre-beta (PAB).
  • PAB pre-beta
  • PCD film stability
  • the resist pattern obtained using the negative resist composition for electron beam of the present invention can be suitably used as a mold (original) for imprint lithography. Therefore, the present invention is extremely useful industrially.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L'invention concerne une nouvelle composition de résist de type négatif pour un faisceau d'électrons. L'invention concerne également un procédé pour la formation d'un motif de résist à l'aide de la composition de résist de type négatif. La composition de résist de type négatif comprend : (A) au moins un composé choisi dans le groupe constitué par un hydrolysat d'un composé alcoxysilane représenté par la formule générale (I) et un produit de condensation du composé alcoxysilane ; et (B) un générateur d'acide non ionique. R1n-Si(OR2)4-n (I) dans laquelle R1 représente un atome d'hydrogène ou un groupe organique ayant une valence de 1; R² représente un groupe organique ayant une valence de 1 ; et n représente un entier de 1 à 3.
PCT/JP2007/064002 2006-09-26 2007-07-13 Composition de résist de type négatif pour un faisceau d'électrons, et procédé de formation d'un motif de résist WO2008038448A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-260805 2006-09-26
JP2006260805A JP4772632B2 (ja) 2006-09-26 2006-09-26 電子線用ネガ型レジスト組成物およびレジストパターン形成方法

Publications (1)

Publication Number Publication Date
WO2008038448A1 true WO2008038448A1 (fr) 2008-04-03

Family

ID=39229888

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/064002 WO2008038448A1 (fr) 2006-09-26 2007-07-13 Composition de résist de type négatif pour un faisceau d'électrons, et procédé de formation d'un motif de résist

Country Status (3)

Country Link
JP (1) JP4772632B2 (fr)
TW (1) TW200830046A (fr)
WO (1) WO2008038448A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5413185B2 (ja) * 2008-12-25 2014-02-12 Ｊｓｒ株式会社 ネガ型感放射線性組成物、硬化パターン形成方法および硬化パターン
JP5393282B2 (ja) * 2009-06-17 2014-01-22 東京応化工業株式会社 ナノインプリント用組成物およびパターン形成方法
JP5381508B2 (ja) * 2009-08-27 2014-01-08 Ｊｓｒ株式会社 ネガ型感放射線性組成物、硬化パターン形成方法及び硬化パターン

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10324748A (ja) * 1997-01-31 1998-12-08 Shin Etsu Chem Co Ltd 高分子シリコーン化合物、化学増幅ポジ型レジスト材料及びパターン形成方法
JP2004190036A (ja) * 1997-08-06 2004-07-08 Shin Etsu Chem Co Ltd 高分子シリコーン化合物、レジスト材料及びパターン形成方法
JP2005266474A (ja) * 2004-03-19 2005-09-29 Tokyo Ohka Kogyo Co Ltd ネガ型レジスト組成物
JP2006154037A (ja) * 2004-11-26 2006-06-15 Toray Ind Inc ネガ型感光性樹脂組成物、それから形成された透明硬化膜、および硬化膜を有する素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10324748A (ja) * 1997-01-31 1998-12-08 Shin Etsu Chem Co Ltd 高分子シリコーン化合物、化学増幅ポジ型レジスト材料及びパターン形成方法
JP2004190036A (ja) * 1997-08-06 2004-07-08 Shin Etsu Chem Co Ltd 高分子シリコーン化合物、レジスト材料及びパターン形成方法
JP2005266474A (ja) * 2004-03-19 2005-09-29 Tokyo Ohka Kogyo Co Ltd ネガ型レジスト組成物
JP2006154037A (ja) * 2004-11-26 2006-06-15 Toray Ind Inc ネガ型感光性樹脂組成物、それから形成された透明硬化膜、および硬化膜を有する素子

Also Published As

Publication number Publication date
JP4772632B2 (ja) 2011-09-14
JP2008083192A (ja) 2008-04-10
TW200830046A (en) 2008-07-16

Similar Documents

Publication Publication Date Title
JP4699140B2 (ja) パターン形成方法
JP5000250B2 (ja) パターン形成方法
JP4881313B2 (ja) レジスト組成物及びレジスト画像の形成方法
US7265234B2 (en) Silsesquioxane compound mixture, method of making, resist composition, and patterning process
US20080312400A1 (en) Composition for forming resist underlayer film, and resist underlayer film
TW201116927A (en) Photoacid generators and photoresists comprising same
WO2006090591A1 (fr) Composition de résist à fonctionnement positif, procédé de formation de motifs de résist et composé
JP4987411B2 (ja) パターン形成方法
JP6255210B2 (ja) レジスト下層膜形成組成物
US20090155714A1 (en) Photosensitive compound and photoresist composition including the same
JP4669698B2 (ja) レジスト材料及びパターン形成方法
JP2009120612A (ja) 感光性化合物及びそれを含むフォトレジスト組成物
WO2008038448A1 (fr) Composition de résist de type négatif pour un faisceau d'électrons, et procédé de formation d'un motif de résist
JP3743491B2 (ja) レジスト材料及びパターン形成方法
TWI352696B (en) Compound, positive resist composition and formatio
KR102610345B1 (ko) 포지티브형 감광성 실록산 조성물 및 이를 사용하여 형성된 경화막
US7695893B2 (en) Photo-sensitive compound and photoresist composition including the same
TWI326009B (en) Positive resist composition, method for forming resist pattern and compound
TW201714875A (zh) 化合物、高分子化合物、光阻組成物及圖案形成方法
JP4279204B2 (ja) ポジ型レジスト組成物およびこれに用いられる化合物
US7947423B2 (en) Photosensitive compound and photoresist composition including the same
JP2008203612A (ja) ネガ型レジスト組成物およびレジストパターン形成方法
JP3666550B2 (ja) 新規高分子シリコーン化合物、化学増幅ポジ型レジスト材料及びパターン形成方法
WO2005057284A1 (fr) Composition de photoresine et procede de formation d'un motif de reserve
KR102626975B1 (ko) 포지티브형 감광성 실록산 조성물 및 이를 사용하여 형성된 경화막

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07790782

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07790782

Country of ref document: EP

Kind code of ref document: A1