WO2010143436A1 - Composé cyclique, matériau à base de photorésist et composition de photorésist - Google Patents

Composé cyclique, matériau à base de photorésist et composition de photorésist Download PDF

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WO2010143436A1
WO2010143436A1 PCT/JP2010/003872 JP2010003872W WO2010143436A1 WO 2010143436 A1 WO2010143436 A1 WO 2010143436A1 JP 2010003872 W JP2010003872 W JP 2010003872W WO 2010143436 A1 WO2010143436 A1 WO 2010143436A1
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group
carbon atoms
substituted
unsubstituted
aliphatic hydrocarbon
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PCT/JP2010/003872
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Japanese (ja)
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柏村孝
蓬田知行
大和田貴紀
塩谷英昭
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出光興産株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—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

Definitions

  • the present invention relates to a novel cyclic compound, particularly a radiation sensitive compound.
  • the present invention also relates to a photoresist base material used in the electrical / electronic field such as a semiconductor and the optical field, and more particularly to a photoresist base material for ultrafine processing.
  • Lithography using extreme ultra-violet light (hereinafter sometimes referred to as EUVL) or electron beam is useful as a high-productivity, high-resolution microfabrication method in the manufacture of semiconductors and the like.
  • EUVL extreme ultra-violet light
  • electron beam is useful as a high-productivity, high-resolution microfabrication method in the manufacture of semiconductors and the like.
  • photoresists with high sensitivity and high resolution It is indispensable to improve the sensitivity of the photoresist from the viewpoint of the productivity and resolution of the desired fine pattern.
  • a photoresist used in the ultrafine processing by EUVL for example, a method using a chemically amplified positive photoresist having a higher concentration of photoacid generator than other resist compounds has been proposed (for example, Patent Document 1).
  • the photoresists of the examples are considered to be limited in processing up to 100 nm exemplified in the case of using an electron beam from the viewpoint of line edge roughness. It is presumed that the main cause of this is that the aggregate of the polymer compounds used as the base material or the three-dimensional shape of each polymer compound molecule is large and affects the production line width and the surface roughness.
  • Patent Document 4 discloses a calix resorcinarene compound.
  • An object of the present invention is to provide a photoresist material with high sensitivity and high resolution.
  • Ar represents an arylene group having 6 to 10 carbon atoms; a group in which two or more arylene groups having 6 to 10 carbon atoms are combined; or an arylene group having 6 to 10 carbon atoms; an alkylene group and an ether bond; A group in which one or more of them are combined.
  • Each R is a group represented by the following formula (II).
  • a 1 is a single bond, an arylene group, an alkylene group, an ether bond, or a group obtained by combining at least two of an arylene group, an alkylene group, and an ether bond.
  • R 3 represents hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted carbon number
  • a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a divalent group thereof (substituted or unsubstituted alkylene group) A substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group
  • R 1 is a group represented by the formula (II), a group similar to the group represented by R 3 or a solubility adjusting group, Of the two R 1 existing on the same aromatic ring, one R 1 is the same group as the group represented by the formula (II) or the group represented by R 3 , and the other is the solubility control. And at least one of R 1 is a group represented by the formula (II).
  • R 2 is hydrogen, a hydroxyl group, a group represented by OR 3 , a group represented by OR 4 (R 4 is a solubility adjusting group), a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom. ] 2.
  • the cyclic compound according to 3 wherein the acid dissociable, dissolution inhibiting group is a substituent having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure, or a bicyclic aliphatic structure and having a molecular weight of 15 to 2,000. 5.
  • OR 3 is any one of the following formulas (III) to (VI).
  • ⁇ is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.
  • ⁇ is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
  • ⁇ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; And an alkoxy group substituted with a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
  • ⁇ is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms. ) 6).
  • the solubility adjusting group for R 1 and R 4 is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms.
  • Ar represents an arylene group having 6 to 10 carbon atoms; a group in which two or more arylene groups having 6 to 10 carbon atoms are combined; or an arylene group having 6 to 10 carbon atoms; an alkylene group and an ether bond; A group in which one or more of them are combined.
  • Each R is a group represented by the following formula (II).
  • a 1 is a single bond, an arylene group, an alkylene group, an ether bond, or a group obtained by combining at least two of an arylene group, an alkylene group, and an ether bond.
  • R 3 represents hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted carbon number
  • a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxyalkyl group, a silyl group, or a divalent group thereof (substituted or unsubstituted alkylene group) A substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group
  • R 1 is a group represented by the formula (II), a group similar to the group represented by R 3 or a solubility adjusting group, Of the two R 1 existing on the same aromatic ring, one R 1 is the same group as the group represented by the formula (II) or the group represented by R 3 , and the other is the solubility adjustment. It is a group.
  • R 2 is hydrogen, a hydroxyl group, a group represented by OR 3 , a group represented by OR 4 (R 4 is a solubility adjusting group), a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom. ] 10.
  • a photoresist composition comprising the photoresist base material according to 8 or 9 and a solvent.
  • the photoresist composition according to 10 further comprising a photoacid generator.
  • FIG. 3 is a diagram showing the result of 1 H-NMR measurement of the cyclic compound (A) obtained in Production Example 1.
  • 2 is a diagram showing the results of 1 H-NMR measurement of a cyclic compound (B) obtained in Example 1.
  • FIG. 3 is a diagram showing the result of 1 H-NMR measurement of the cyclic compound (C) obtained in Example 2.
  • FIG. 3 is a diagram showing the result of 1 H-NMR measurement of a cyclic compound (D) obtained in Comparative Example 1.
  • FIG. 4 is a diagram showing the results of 1 H-NMR measurement of the cyclic compound (E) obtained in Example 3.
  • FIG. 3 is a diagram showing the results of 1 H-NMR measurement of a cyclic compound (F) obtained in Comparative Example 2.
  • the cyclic compound of the present invention has a structure represented by the following formula (I).
  • Ar represents an arylene group having 6 to 10 carbon atoms; a group in which two or more arylene groups having 6 to 10 carbon atoms are combined; or an arylene group having 6 to 10 carbon atoms, an alkylene group, and an ether A group in which at least one of the bonds (—O—) is combined.
  • phenylene group, methylphenylene group, dimethylphenylene group, trimethylphenylene group, tetramethylphenylene group, naphthylene group, biphenylene group, and oxydiphenylene group are preferable.
  • a phenylene group, a biphenylene group, and an oxydiphenylene group are preferable.
  • Each R is a group represented by the following formula (II).
  • a 1 in the formula (II) is a single bond, an arylene group, an alkylene group, an ether bond, or a group obtained by combining two or more of an arylene group, an alkylene group, and an ether bond.
  • An alkylene group, an ether bond, or a group in which two or more alkylene groups and ether bonds are combined is preferable.
  • the arylene group include the same groups as the above Ar.
  • the alkylene group those having 1 to 4 carbon atoms such as a methylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a butylene group are preferable.
  • the group in which two or more alkylene groups and ether bonds are combined is preferably an oxymethylene group, an oxydimethylmethylene group, an oxyethylene group, an oxypropylene group, or an oxybutylene group.
  • a 1 is preferably a single bond or an oxymethylene group (—O—CH 2 —).
  • R 3 represents hydrogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted carbon, respectively.
  • linear aliphatic hydrocarbon group having 1 to 20 carbon atoms a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like are preferable.
  • branched aliphatic hydrocarbon group having 3 to 12 carbon atoms a t-butyl group, an iso-propyl group, an iso-butyl group, a 2-ethylhexyl group, and the like are preferable.
  • cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms a cyclohexyl group, norbornyl group, adamantyl group, biadamantyl group, diamantyl group and the like are preferable.
  • aromatic group having 6 to 10 carbon atoms a phenyl group, a naphthyl group, and the like are preferable.
  • alkoxyalkyl group a methoxymethyl group, an ethoxymethyl group, an adamantyloxymethyl group and the like are preferable.
  • silyl group a trimethylsilyl group, a t-butyldimethylsilyl group and the like are preferable.
  • each of the above groups may have a substituent, specifically, an alkyl group such as a methyl group or an ethyl group, a ketone group, an ester bond, an alkoxy group, a nitrile group, a nitro group, or a hydroxyl group.
  • an alkyl group such as a methyl group or an ethyl group, a ketone group, an ester bond, an alkoxy group, a nitrile group, a nitro group, or a hydroxyl group.
  • R 3 may be a group having a structure in which each of the above groups and a divalent group are bonded.
  • the divalent group include a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or one or more of these groups.
  • the alkylene group is preferably a methylene group, a methylmethylene group or the like, and the arylene group is preferably a phenylene group.
  • each R ′ represents H or an alkyl group.
  • OR 3 is preferably an acid dissociable, dissolution inhibiting group, and more preferably a substituent having an aromatic structure, a monocyclic aliphatic structure, or a bicyclic aliphatic structure and having a molecular weight of 15 or more and 2000 or less.
  • OR 3 is any one of the following formulas (III) to (VI) is preferable.
  • ⁇ is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms or a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms.
  • ⁇ is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
  • ⁇ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; And an alkoxy group substituted with a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
  • ⁇ is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.
  • y of Formula (I) is 1. It is also preferred that x in the formula (II) is 1.
  • Ar is preferably a phenyl group.
  • a 1 is preferably a single bond.
  • acid dissociable, dissolution inhibiting group examples include groups represented by the following formulae.
  • r represents any of the substituents having no r among the substituents represented by the above formula.
  • x is an integer of 1 to 5, and preferably an integer of 1 to 3.
  • y is an integer of 0 to 3, and is preferably 1 or 2.
  • formula (I) there are a plurality of R, but each R 3 , Ar, A 1 , x and y constituting R may be the same or different.
  • the formula (II) is preferably any one of the following formulas. (Wherein R 3 represents the same group as in formula (II), and x is an integer of 1 to 5)
  • R 1 is a group represented by the formula (II), a group similar to the group represented by the R 3 or a solubility adjusting group.
  • one R 1 is a group similar to the group represented by the formula (II) or the group represented by R 3 described above, Is a solubility adjusting group, and at least one of R 1 is a group represented by the formula (II).
  • the formula (II) II when all four R 1 except for the solubility adjusting group are formula (II), three are formula (II), two are formula (II), one is formula (II) II).
  • two of the four R 1 are of formula (II), and one of the four R 1 is of formula (II).
  • hydrophilicity becomes high and adhesiveness with a photoresist substrate improves. More preferably, only one of the four R 1 is formula (II).
  • R 1 is a group similar to the group represented by R 3
  • preferred examples of R 1 are the same as the preferred examples of R 3 .
  • Particularly preferred are the case where all R 3 present in R 1 is hydrogen and the case where R 3 present in R 1 coexists with hydrogen and an acid dissociable, dissolution inhibiting group.
  • Specific examples of the acid dissociable, dissolution inhibiting group are the same as described above.
  • the solubility adjusting group is preferably a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted group.
  • Preferred examples of each group of dissolution controlling group is the same as R 3 as described above.
  • R 2 is hydrogen, a hydroxyl group, a group represented by OR 3 , a group represented by OR 4 (R 4 is a solubility adjusting group), a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.
  • R 3 is the same as R 3 described above.
  • Suitable examples of the solubility adjusting group are the same as those for R 1 described above.
  • the group containing an oxygen atom is preferably a group represented by OR 3 , a group represented by OR 4 (R 4 is a solubility adjusting group), an alkoxy group, an alkoxycarbonyl group, or the like.
  • R 2 is hydrogen.
  • a plurality of R, R 1 and R 2 in the formula (I) may be the same or different.
  • the acid dissociable, dissolution inhibiting group has high reactivity to EUVL and electron beam, it is excellent in sensitivity and etching resistance. Therefore, when the cyclic compound contains an acid dissociable, dissolution inhibiting group, it can be suitably used as a photoresist substrate for ultrafine processing.
  • the cyclic compound according to the present invention can be obtained by, for example, a calix resorcinol reaction by a condensation cyclization reaction between an aldehyde compound having a corresponding structure and an aromatic compound having both a solubility adjusting group and a hydroxyl group in the presence of an acid catalyst by a known method. It can be synthesized by synthesizing a len derivative (precursor) and introducing a compound corresponding to a group such as R 3 into the precursor by an esterification reaction, an etherification reaction, an acetalization reaction or the like. Specific examples will be described in the embodiments described later.
  • the cyclic compound according to the present invention is useful as a photoresist base material, particularly as a photoresist base material used in ultra-fine processing by lithography such as extreme ultraviolet light (wavelength 15 nm or less) or electron beam.
  • the cyclic compound according to the present invention is used for a photoresist substrate, it is refined and basic impurities (for example, alkali metal ions such as ammonia, Li, Na and K, alkaline earth metal ions such as Ca and Ba, etc.), etc. Is preferably removed.
  • basic impurities for example, alkali metal ions such as ammonia, Li, Na and K, alkaline earth metal ions such as Ca and Ba, etc.
  • the content of basic impurities is preferably 10 ppm or less, more preferably 2 ppm or less.
  • Examples of the purification method include a method of treating by reprecipitation using acidic aqueous solution washing, ion exchange resin, or ultrapure water. You may refine
  • the cyclic compound of the present invention preferably contains an alkali-soluble group because the solubility in an alkali developer is increased by the action of an acid.
  • alkali-soluble group examples include a hydroxyl group, a sulfonic acid group, a phenol group, a carboxyl group, and a hexafluoroisopropanol group [—C (CF 3 ) 2 OH].
  • Preferred are a phenol group, a carboxyl group, and a hexafluoroisopropanol group, and more preferred are a phenol group and a carboxyl group.
  • the cyclic compound of the present invention can be used as a photoresist base material used in ultra-fine processing by lithography such as extreme ultraviolet light or an electron beam.
  • the photoresist base material of other embodiment of this invention contains the cyclic compound represented by following formula (I '), and the number of group represented by the following formula (II) which 1 molecule of cyclic compounds has. Is more than 4 and 8 or less. [Wherein, R is a group represented by the following formula (II).
  • R 1 to R 3 , Ar, A 1 , x, y represent the same groups as in the examples of the above formulas (I) and (II).
  • R 1 is the same group as the group represented by the formula (II) or the group represented by R 3 , and the other is the solubility control. It is a group.
  • the average number of groups represented by the following formula (II) contained in one molecule of the cyclic compound is more than 4 and 8 or less. That is, in addition to the four Rs that the compound of formula (I) has, at least a part of R 1 has a group represented by formula (II). Preferably, it is more than 4 and 6 or less, and particularly preferably more than 4 and 5 or less.
  • the average number of the formula (II) is 6.0 or less, the hydrophilicity becomes high and the adhesion with the photoresist substrate is improved. If R 1 of the cyclic compound in the composition is the formula (II), the sensitivity is improved, but the above range is preferable from the viewpoint of adhesion to the substrate.
  • the compound of the formula (I ′) it is preferable that two or one of the four R 1 excluding the solubility-controlling group is a group of the formula (II), and in particular, of the four R 1 , Preferred is the case where only one is of formula (II).
  • the average number of groups represented by the formula (II) contained in one molecule of the cyclic compound is calculated from an NMR spectrum and liquid chromatography.
  • the photoresist composition of this invention contains said photoresist base material and a solvent.
  • the compounding amount of the cyclic compound is preferably 50 to 99.9% by weight, more preferably 75 to 95% by weight in the total composition excluding the solvent.
  • a cyclic compound When a cyclic compound is used as a photoresist base material, it may be used alone or in combination of two or more, as long as the effects of the present invention are not impaired.
  • Examples of the solvent used in the photoresist composition of the present invention include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like.
  • Ethylene glycol monoalkyl ethers propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; propylene glycols such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether Monoalkyl ethers; methyl lactate, ethyl lactate ( L) Lactic acid esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and ethyl propionate (PE); methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -Other esters such as methyl ethoxypropionate and ethyl 3-ethoxypropionate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-hept
  • the components other than the solvent in the composition that is, the amount of the photoresist solid content, is preferably set to an amount suitable for forming a desired thickness of the photoresist layer. Specifically, it is generally 0.1 to 50% by weight of the total weight of the photoresist composition, but it can be defined according to the type of base material and solvent used, or the desired film thickness of the photoresist layer. .
  • the solvent is preferably blended in an amount of 50 to 99.9% by weight in the total composition.
  • the photoresist composition of the present invention may consist essentially of a photoresist base material composed of the cyclic compound of the present invention and a solvent, or may comprise only these components. “Substantially” means that the composition consists only of a photoresist base material and a solvent and can contain the following additives in addition to these components.
  • the photoresist composition of the present invention does not require an additive particularly when the substrate molecule contains a chromophore active against EUV and / or electron beam and exhibits the ability as a photoresist alone.
  • a photoacid generator (PAG) or the like is generally included as a chromophore as necessary.
  • the photoacid generator is not particularly limited, and those proposed as acid generators for chemically amplified resists can be used.
  • acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and diazomethanes such as poly (bissulfonyl) diazomethanes.
  • onium salt acid generators such as iodonium salts and sulfonium salts
  • oxime sulfonate acid generators such as bisalkyl or bisarylsulfonyldiazomethanes
  • diazomethanes such as poly (bissulfonyl) diazomethanes.
  • acid generators nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the
  • Examples of the onium salt acid generator include acid generators represented by the following formula (b-0).
  • R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group
  • R 52 represents a hydrogen atom, a hydroxyl group, a halogen atom, linear or A branched alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group
  • R 53 is an optionally substituted aryl group
  • u '' Is an integer of 1 to 3.
  • R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
  • the linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
  • the fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • the fluorination rate of the fluorinated alkyl group (ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, and particularly hydrogen. Those in which all atoms are substituted with fluorine atoms are preferred because the strength of the acid is increased.
  • R 51 is most preferably a linear alkyl group or a fluorinated alkyl group.
  • R 52 represents a hydrogen atom, a hydroxyl group, a halogen atom, a linear, branched or cyclic alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group.
  • examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3.
  • the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms.
  • the alkyl group herein are the same as the “alkyl group” in R 52 .
  • the halogen atom to be substituted include the same as those described above for the “halogen atom”.
  • the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3. Of these, R 52 is preferably a hydrogen atom.
  • R 53 is an aryl group which may have a substituent, and examples of the structure of the basic ring (matrix ring) excluding the substituent include a naphthyl group, a phenyl group, an anthracenyl group, and the like. From the viewpoint of absorption of exposure light such as ArF excimer laser or the like, a phenyl group is desirable.
  • the substituent include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
  • the aryl group for R 53 an aryl group having no substituent is more preferable.
  • U ′′ is an integer of 1 to 3, preferably 2 or 3, and particularly preferably 3.
  • Preferable examples of the acid generator represented by the formula (b-0) include those represented by the following chemical formula.
  • the acid generator represented by the formula (b-0) can be used alone or in combination.
  • Examples of the onium salt acid generator other than the acid generator represented by the formula (b-0) include compounds represented by the following formula (b-1) or (b-2). [Wherein R 1 ′′ to R 3 ′′, R 5 ′′, R 6 ′′ each independently represents a substituted or unsubstituted aryl group or alkyl group; R 4 ′′ represents a linear, branched or cyclic group; Represents an alkyl group or a fluorinated alkyl group; at least one of R 1 ′′ to R 3 ′′ represents an aryl group, and at least one of R 5 ′′ and R 6 ′′ represents an aryl group.]
  • R 1 ′′ to R 3 ′′ each independently represents a substituted or unsubstituted aryl group or alkyl group. At least one of R 1 ′′ to R 3 ′′ represents a substituted or unsubstituted aryl group. Of R 1 ′′ to R 3 ′′, two or more are preferably substituted or unsubstituted aryl groups, and most preferably all of R 1 ′′ to R 3 ′′ are substituted or unsubstituted aryl groups.
  • the aryl group for R 1 ′′ to R 3 ′′ is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, alkoxy groups It may or may not be substituted with a group, a halogen atom or the like.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.
  • the alkyl group which is a substituent of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
  • the alkoxy group which is a substituent of the aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and most preferably a methoxy group or an ethoxy group.
  • the halogen atom that is a substituent of the aryl group is preferably a fluorine atom.
  • the alkyl group for R 1 ′′ to R 3 ′′ is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decanyl group and the like. A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost. Among these, it is most preferable that all of R 1 ′′ to R 3 ′′ are phenyl groups.
  • R 4 ′′ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
  • the linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group is a cyclic group as represented by R 1 ′′, preferably having 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and more preferably 6 carbon atoms. Most preferably, it is ⁇ 10.
  • the fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. Also.
  • the fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, and in particular, those in which all hydrogen atoms are substituted with fluorine atoms. This is preferable because the strength of the acid is increased.
  • R 4 ′′ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
  • R 5 ′′ and R 6 ′′ each independently represents a substituted or unsubstituted aryl group or alkyl group. At least one of R 5 ′′ and R 6 ′′ represents a substituted or unsubstituted aryl group. All of R 5 ′′ and R 6 ′′ are preferably substituted or unsubstituted aryl groups. Examples of the substituted or unsubstituted aryl group for R 5 ′′ to R 6 ′′ include those similar to the substituted or unsubstituted aryl group for R 1 ′′ to R 3 ′′. As the alkyl group for R 5 ′′ to R 6 ′′, the same as the alkyl groups for R 1 ′′ to R 3 ′′ can be used. Of these, it is most preferable that all of R 5 ′′ to R 6 ′′ are phenyl groups. "As R 4 in the formula (b-1)" R 4 in the In the formula (b-2) include the same as.
  • onium salt acid generators represented by the formulas (b-1) and (b-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium.
  • Trifluoromethanesulfonate or nonafluorobutanesulfonate triphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, tri (4-methylphenyl) sulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or the same Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropropyl Pansulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanes
  • onium salts in which the anion portion of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.
  • an onium salt acid generator in which the anion moiety is replaced by the anion moiety represented by the following formula (b-3) or (b-4) in the formula (b-1) or (b-2) is also used.
  • the cation moiety is the same as (b-1) or (b-2)).
  • X ′′ is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, Preferably it is C3.
  • Y ′′ and Z ′′ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably It has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the number of carbon atoms of the alkylene group of X ′′ or the number of carbon atoms of the alkyl group of Y ′′ and Z ′′ is preferably as small as possible because the solubility in a resist solvent is good within the above-mentioned range of carbon numbers.
  • the strength of the acid increases as the number of hydrogen atoms substituted by fluorine atoms increases, and high-energy light or electron beam of 200 nm or less
  • the ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all.
  • compounds represented by the following formulas (30) to (35) can also be used as a photoacid generator.
  • Q is an alkylene group, an arylene group or an alkoxylene group
  • R 15 is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.
  • the compound represented by the formula (30) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- ( 0-camphorsulfonyl
  • R 16 may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.
  • the compound represented by the formula (31) includes diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, di It is at least one selected from the group consisting of (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-toluromethylphenyl) disulfone. preferable.
  • R 17 may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.
  • the compound represented by the formula (32) includes ⁇ - (methylsulfonyloxyimino) -phenylacetonitrile, ⁇ - (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, ⁇ - (trifluoromethylsulfonyloxyimino) -phenyl.
  • R 18 may be the same or different and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms.
  • the halogenated alkyl group preferably has 1 to 5 carbon atoms.
  • R 19 and R 20 are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopentyl group, or a cyclohexyl group.
  • a cycloalkyl group such as methoxy group, ethoxy group, propoxy group or the like, or an aryl group such as phenyl group, toluyl group or naphthyl group, preferably 6 to 10 carbon atoms.
  • L 19 and L 20 are each independently an organic group having a 1,2-naphthoquinonediazide group.
  • organic group having a 1,2-naphthoquinonediazide group examples include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- Preferred examples include 1,2-quinonediazidosulfonyl groups such as a 6-sulfonyl group.
  • 1,2-naphthoquinonediazido-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable.
  • J 19 is a group having a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (34a), a carbonyl bond, an ester bond, an amide bond or an ether bond.
  • Y 19 is each independently a hydrogen atom, an alkyl group or an aryl group, and X 20 is each independently a group represented by the following formula (35a).
  • each of Z 22 independently represents an alkyl group, a cycloalkyl group or an aryl group, each of R 22 independently represents an alkyl group, a cycloalkyl group or an alkoxy group, and r represents 0 to 3 It is an integer.
  • Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1,4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6
  • a compound that generates an organic sulfonic acid by the action of actinic rays or radiation is particularly preferable.
  • the blending amount of PAG is 0 to 40% by weight, preferably 5 to 30% by weight, and more preferably 5 to 20% by weight in the total composition excluding the solvent.
  • an acid diffusion control agent having an action of controlling an undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film.
  • an acid diffusion controller By using such an acid diffusion controller, the storage stability of the photoresist composition is improved. Further, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before electron beam irradiation and the holding time after electron beam irradiation can be suppressed, and the process stability is extremely excellent.
  • acid diffusion control agents include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, Isopropano Electron beam radiation decom
  • the blending amount of the quencher is 0 to 40% by weight, preferably 0.01 to 15% by weight in the total composition excluding the solvent.
  • miscible additives for example, additional resins for improving the performance of resist films, surfactants for improving coating properties, dissolution control agents, sensitizers, plasticizers. Stabilizers, colorants, antihalation agents, dyes, pigments, and the like can be appropriately added and contained.
  • the dissolution controlling agent is a component having an action of reducing the solubility of the cyclic compound in an alkaline developer so as to moderate the dissolution rate during development.
  • dissolution control agent examples include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone.
  • aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene
  • ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone
  • sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone.
  • bisphenols into which an acid dissociable functional group has been introduced tris (hydroxyphenyl) methane into
  • dissolution control agents can be used alone or in combination of two or more.
  • the blending amount of the dissolution control agent is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 50% by weight, more preferably 0 to 40% by weight, and more preferably 0 to 30% by weight based on the total weight of the solid component. Is more preferable.
  • the sensitizer is a component that absorbs the energy of the irradiated radiation and transmits the energy to the acid generator, thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist. is there.
  • Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more.
  • the blending amount of the sensitizer is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, and further preferably 0 to 10% by weight based on the total weight of the solid component.
  • the surfactant is a component having an action of improving the coating property and striation of the photoresist composition of the present invention, the developability as a resist, and the like.
  • a surfactant any of anionic, cationic, nonionic or amphoteric can be used. Of these, nonionic surfactants are preferred. Nonionic surfactants have better affinity with the solvent used in the photoresist composition and are more effective.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names: Ftop (manufactured by Gemco) , MegaFac (Dainippon Ink & Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), Pepol (Toho Chemical), KP (Shin-Etsu Chemical)
  • the series products such as Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and the like can be mentioned, but are not particularly limited.
  • the compounding amount of the surfactant is preferably 0 to 2% by weight, more preferably 0 to 1% by weight, and further preferably 0 to 0.1% by weight based on the total weight of the solid component.
  • the latent image in the exposed area can be visualized and the influence of halation during exposure can be mitigated. Furthermore, the adhesiveness with a board
  • An organic carboxylic acid or phosphorus oxo acid or a derivative thereof is added as an optional component for the purpose of preventing sensitivity deterioration when an acid diffusion control agent is added and improving the resist pattern shape, retention stability, etc. be able to. These compounds can be used in combination with an acid diffusion controller or may be used alone.
  • the organic carboxylic acid for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives thereof, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- Examples include phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester or derivatives thereof, phosphinic acids such as phosphinic acid and phenylphosphinic acid, and derivatives thereof. Of these, phosphonic acid is particularly preferred.
  • the photoresist composition of the present invention is applied onto a substrate such as a silicon wafer, a gallium arsenide wafer, or a wafer coated with aluminum, by spin coating, cast coating, roll coating, or other coating means. Then, a resist film is formed by coating.
  • a surface treatment agent may be applied on the substrate in advance.
  • the surface treatment agent include a silane coupling agent such as hexamethylene disilazane (hydrolyzable polymerizable silane coupling agent having a polymerizable group), an anchor coating agent or a base agent (polyvinyl acetal, acrylic resin, vinyl acetate). Based resins, epoxy resins, urethane resins, etc.), and coating agents obtained by mixing these base agents and inorganic fine particles.
  • a protective film may be formed on the resist film in order to prevent invasion of amines floating in the atmosphere.
  • the acid generated in the resist film due to radiation reacts with a compound that reacts with an acid such as amine floating as an impurity in the atmosphere and deactivates, and the resist image deteriorates and sensitivity. Can be prevented from decreasing.
  • a water-soluble and acidic polymer is preferable. Examples thereof include polyacrylic acid and polyvinyl sulfonic acid.
  • the heating temperature varies depending on the composition of the photoresist composition, but is preferably 20 to 250 ° C., more preferably 40 to 150 ° C.
  • the resist film is exposed to a desired pattern by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray.
  • the exposure conditions and the like are appropriately selected according to the composition of the photoresist composition.
  • the post-exposure heating temperature (PEB) varies depending on the composition of the photoresist composition, but is preferably 20 to 250 ° C., more preferably 40 to 150 ° C.
  • a predetermined resist pattern can be formed by developing the exposed resist film with an alkaline developer.
  • the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline.
  • An alkaline aqueous solution of preferably 1 to 10% by weight, more preferably 1 to 5% by weight, in which one or more compounds are dissolved, is used.
  • An appropriate amount of an alcohol such as methanol, ethanol, isopropyl alcohol, or the above-mentioned surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by weight of isopropyl alcohol.
  • the resist film is exposed to a desired pattern with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray, thereby generating an acid.
  • radiation such as KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray
  • the dissociable dissolution inhibiting group is eliminated or the structure is changed, the dissociable dissolution inhibiting group is dissolved in the alkaline developer.
  • it is preferable that the unexposed portion of the pattern is not dissolved in the alkaline developer.
  • the non-solubility in the alkali developer cannot be generally defined because the preferred non-solubility differs depending on the development conditions such as the size of the pattern to be formed and the type of the alkali developer to be used.
  • the insolubility expressed by the developer dissolution rate of a thin film made of a photoresist substrate is preferably less than 1 nanometer / second, preferably 0.5 nanometer / second. Less than a second is particularly preferred.
  • post-baking treatment may be included after the alkali development, and an organic or inorganic antireflection film may be provided between the resist film and the substrate.
  • the pattern wiring board is obtained by etching. Etching can be performed by a known method such as dry etching using plasma gas, wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like. After the resist pattern is formed, a plating process such as copper plating, solder plating, nickel plating, or gold plating can be performed.
  • the residual resist pattern after etching can be stripped with an aqueous solution stronger than an organic solvent or an alkali developer.
  • organic solvent include PGMEA, PGME, EL, acetone, tetrahydrofuran, and the like.
  • strong alkaline aqueous solution include 1 to 20% by weight sodium hydroxide aqueous solution and 1 to 20% by weight potassium hydroxide aqueous solution. Is mentioned.
  • peeling method include a dipping method and a spray method.
  • the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.
  • a wiring board by a method of forming a resist pattern using the photoresist composition of the present invention, vacuum depositing a metal, and then eluting the resist pattern with a solution, that is, a lift-off method.
  • the ultrafine processing by lithography of extreme ultraviolet light or electron beam can be performed using the photoresist composition according to the present invention.
  • semiconductor devices such as ULSIs, large-capacity memory devices, and ultrahigh-speed logic devices can be manufactured.
  • the performance of the above-mentioned ULSI, large-capacity memory device, ultrahigh-speed logic device, etc. can be dramatically improved by the microfabrication method of the present invention. Furthermore, by incorporating semiconductor devices manufactured using the photoresist composition of the present invention as parts, the performance of semiconductor embedded products such as information home appliances, computer devices, memory devices such as USB memory, display devices, etc. Can be improved.
  • the degree of protection is determined by protons of methylene sandwiched between the benzene ring on the side where no ring is formed around 6.6 ppm and 7.5 ppm, and both esters in the protecting group near 4.8 ppm. It calculated from the integrated value, and also calculated by analyzing by liquid chromatography. The average number of groups represented by the formula (II) was 4.24 (protection rate ⁇ 8).
  • Example 2 [Synthesis of Compound C] Under a nitrogen stream, ethyl adamantyl bromoacetate 4 was added to a mixture of 3.0 g (2.93 mmol) of the cyclic compound (A) prepared in Production Example 1, 1.64 g (15.5 mmol) of sodium carbonate and 100 ml of dimethylformamide. After dropwise addition of .65 g (15.5 mmol), the mixture was stirred with heating at 80 ° C. for 8 hours. The reaction mixture was allowed to cool and the white precipitate precipitated by adding water was filtered off to obtain 2.0 g of cyclic compound C. The results of 1 H-NMR measurement are shown in FIG. It was confirmed that the structure was as follows. The average number of groups represented by the formula (II) was 5.2.
  • cyclic compound A (1.00 g, 1.00 mmol) prepared in Production Example 1 was added to form a nitrogen atmosphere, and then anhydrous N-methyl-2-pyrrolidone (40 ml) was added. Further, the mixture was stirred at room temperature, ethyl adamantyl bromoacetate (1.50 g, 5.00 mmol) diluted with triethylamine (0.7 ml, 5.00 mmol) and anhydrous N-methyl-2-pyrrolidone (1 ml), And 1,8-diazabicyclo [5,4,0] -7-undecene (0.22 ml, 1.50 mmol) was added dropwise.
  • Example 3 [Synthesis of Compound E] After adding the cyclic compound (1) prepared in Production Example 1 (1.00 g, 1.00 mmol) to a 200 ml two-necked flask under a nitrogen atmosphere, anhydrous N-methyl-2-pyrrolidone (40 ml) ) And stirred at room temperature, and diluted with triethylamine (0.7 ml, 5.00 mmol) and anhydrous N-methyl-2-pyrrolidone (1 ml) 2-bromoacetic acid 1-ethylcyclohexyl (1.25 g, 5.00 mmol) and 1,8-diazabicyclo [5,4,0] -7-undecene (0.37 ml, 2.5 mmol) were added dropwise.
  • a photoresist solution composed of a substrate, PAG, quencher, and solvent was prepared, and a pattern was formed on a silicon wafer using an electron beam.
  • 77 parts by weight of each of the compounds obtained in Example 1-3 and Comparative Examples 1 and 2 were used as the base material, and triphenylsulfonium nonafluorobutane sulfonate was used as the PAG, as shown in Table 1, respectively.
  • 4 parts by weight of 4-diazabicyclo (2,2,2) octane was used.
  • These solid components were dissolved in propylene glycol monomethyl ether so as to have a concentration of 2.5% by weight.
  • the photoresist solutions containing the compounds obtained in Example 1-3 and Comparative Examples 1 and 2 are each spin-coated on a silicon wafer subjected to hexamethyldisilazane (HMDS) treatment and pre-baked (pre-exposure baking). As a result, a thin film was formed.
  • the substrate having this thin film was drawn using an electron beam drawing apparatus (acceleration voltage 50 kV), PEB (post-exposure baking), and then a 60% aqueous solution of tetrabutylammonium hydroxide having a concentration of 2.38 wt%. The film was developed for 2 seconds, washed with pure water for 60 seconds, and then dried with a nitrogen stream.
  • Table 1 shows the resolution (half pitch) and sensitivity (necessary electron beam dose) obtained when a line / space pattern having a size of 1/1 was obtained from the observation result by a scanning electron microscope. The results were the same even when tri-n-octylamine was used in place of 1,4-diazabicyclo (2,2,2) octane as the quencher.
  • the substrate having the photoresist thin film was irradiated with EUV light (wavelength: 13.5 nm) using an EUV exposure apparatus instead of the electron beam drawing apparatus. Thereafter, a post-processing operation similar to that at the time of electron beam drawing was performed. When observed with a scanning electron microscope, it was observed that the resolution was the same as in the case of electron beam drawing.
  • the cyclic compound of the present invention can be suitably used for a photoresist substrate or composition, particularly for an extreme ultraviolet light and / or an electron beam photoresist substrate or composition.
  • the cyclic compound of the present invention can also be used as an additive for adjusting the solubility.
  • the photoresist base material and the composition thereof of the present invention are suitably used in the electric / electronic field and the optical field such as semiconductor devices.

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Abstract

Composé cyclique représenté par la formule (I).
PCT/JP2010/003872 2009-06-11 2010-06-10 Composé cyclique, matériau à base de photorésist et composition de photorésist WO2010143436A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003321423A (ja) * 2002-05-09 2003-11-11 Jsr Corp カリックスレゾルシンアレーン誘導体および感放射線性樹脂組成物
JP2008116677A (ja) * 2006-11-02 2008-05-22 Mitsubishi Gas Chem Co Inc レジスト下層膜形成材料及び多層レジストパターン形成方法
WO2008153154A1 (fr) * 2007-06-15 2008-12-18 Idemitsu Kosan Co., Ltd. Composé cyclique, matériau de base pour résine photosensible et composition pour résine photosensible
JP2009173625A (ja) * 2007-05-09 2009-08-06 Mitsubishi Gas Chem Co Inc 感放射線性組成物、化合物、化合物の製造方法およびレジストパターン形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003321423A (ja) * 2002-05-09 2003-11-11 Jsr Corp カリックスレゾルシンアレーン誘導体および感放射線性樹脂組成物
JP2008116677A (ja) * 2006-11-02 2008-05-22 Mitsubishi Gas Chem Co Inc レジスト下層膜形成材料及び多層レジストパターン形成方法
JP2009173625A (ja) * 2007-05-09 2009-08-06 Mitsubishi Gas Chem Co Inc 感放射線性組成物、化合物、化合物の製造方法およびレジストパターン形成方法
WO2008153154A1 (fr) * 2007-06-15 2008-12-18 Idemitsu Kosan Co., Ltd. Composé cyclique, matériau de base pour résine photosensible et composition pour résine photosensible

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HIROTO KUDO ET AL., BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 77, no. 11, 2004, pages 2109 - 2114 *

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