WO2011037071A1 - Composé cyclique, composition sensible au rayonnement, et procédé de formation de motif de réserve - Google Patents

Composé cyclique, composition sensible au rayonnement, et procédé de formation de motif de réserve Download PDF

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Publication number
WO2011037071A1
WO2011037071A1 PCT/JP2010/066092 JP2010066092W WO2011037071A1 WO 2011037071 A1 WO2011037071 A1 WO 2011037071A1 JP 2010066092 W JP2010066092 W JP 2010066092W WO 2011037071 A1 WO2011037071 A1 WO 2011037071A1
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group
radiation
carbon atoms
sensitive composition
cyclic compound
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PCT/JP2010/066092
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English (en)
Japanese (ja)
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悠 岡田
宏美 林
雅敏 越後
大 小黒
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三菱瓦斯化学株式会社
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Priority to JP2011532982A priority Critical patent/JPWO2011037071A1/ja
Publication of WO2011037071A1 publication Critical patent/WO2011037071A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition

Definitions

  • the present invention relates to a cyclic compound represented by a specific chemical structural formula, useful as an acid amplification type non-polymeric resist material, a radiation sensitive composition containing the same, and a resist pattern forming method using the composition.
  • Conventional general resist materials are polymer materials capable of forming an amorphous thin film.
  • a resist thin film prepared by applying a solution of a polymer resist material such as polymethyl methacrylate, polyhydroxystyrene having an acid-dissociable reactive group or polyalkyl methacrylate on a substrate, ultraviolet rays, far ultraviolet rays, electron beams, extreme A line pattern of about 45 to 100 nm is formed by irradiating with ultraviolet rays (EUV), X-rays or the like.
  • EUV ultraviolet rays
  • polymer resists have a large molecular weight of about 10,000 to 100,000 and a wide molecular weight distribution.
  • an alkali developing negative radiation-sensitive composition (see Patent Document 3 and Non-Patent Document 1) using a low molecular weight cyclic polyphenol compound as a main component has been proposed. Since these low molecular weight cyclic polyphenol compounds have a low molecular weight, it is expected to provide a resist pattern having a small molecular size, high resolution, and low roughness. Further, the low molecular weight cyclic polyphenol compound has a rigid cyclic structure in its skeleton, and thus provides high heat resistance despite its low molecular weight. However, currently known low molecular weight cyclic polyphenol compounds have problems such as low solubility in safety solvents used in semiconductor manufacturing processes, low sensitivity, and poor resist pattern shape. Improvement of polyphenol compounds is desired.
  • An object of the present invention is to provide a cyclic compound that gives a high-sensitivity and good resist pattern shape, a radiation-sensitive composition containing the same, and a resist pattern forming method using the radiation-sensitive composition. .
  • a cyclic compound having a specific structure has a high solubility in safety solvent solubility, high sensitivity, and a good resist pattern shape.
  • a trans cyclic compound represented by the following formula (1) (In the formula (1), L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms.
  • R 1 is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cyano group, or a nitro group.
  • R ′ is independently an alkyl group having 2 to 20 carbon atoms or the following formula (Wherein R 4 is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, A hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, or an alkylsilyl group having 1 to 20 carbon atoms, and p is an integer of 0 to 5) Is an aryl group represented by: )
  • trans cyclic compound according to item 1 represented by the following formula (2).
  • R 1 , R 4 , p and m are the same as described above.
  • X 2 is a hydrogen or halogen atom
  • m 5 is an integer of 0 to 3
  • m + m 5 4.
  • trans cyclic compound according to item 2 represented by the following formula (3-1) or (3-2): (In the formulas (3-1) and (3-2), R 1 , R 4 , X 2 , and p are the same as described above. M 3 is 1 or 2, and m 4 is 1. )
  • trans cyclic compound according to item 4 represented by the following formula (5-1a) or (5-1b): (In formulas (5-1a) and (5-1b), X 2 , R 4 , m 3 , m 4 , and p are the same as described above.)
  • a radiation-sensitive composition comprising a cyclic compound containing the trans cyclic compound according to any one of items 1 to 6 and a cis isomer thereof in a ratio of 80 to 100: 0 to 20 and a solvent.
  • the radiation-sensitive composition according to claim 7, comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent.
  • the cyclic compound is at least one aldehyde compound (A1) having 2 to 59 carbon atoms having 1 to 4 formyl groups and at least one having 6 to 15 carbon atoms having 1 to 3 phenolic hydroxyl groups.
  • the radiation-sensitive composition according to any one of Items 7 to 9, which is synthesized by a condensation reaction with a phenol compound (A2) and has a molecular weight of 700 to 5,000.
  • Acid is generated directly or indirectly by irradiation with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam, or heat.
  • any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam, or heat.
  • the radiation sensitive composition according to any one of items 7 to 11, further comprising an acid generator (C).
  • the cyclic compound is obtained by a condensation reaction of two or more benzaldehyde compounds having 7 to 24 carbon atoms and two or more phenol compounds (A2) having 6 to 15 carbon atoms having 1 to 3 phenolic hydroxyl groups.
  • the solid component is a cyclic compound / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) in a weight percentage of 50 to 99.99% based on the solid component.
  • the radiation-sensitive composition according to item 8 which contains 4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49/0 to 49.
  • the trans form has a two-fold symmetry (C 2V ) represented by the following formulas (12-1) and (12-2), and is a cis-trans-trans (ctt) It shows the structure of the chair type configuration shown.
  • C 2V two-fold symmetry
  • ctt cis-trans-trans
  • a resist pattern forming method can be provided.
  • Cyclic Compound The trans cyclic compound of the present invention is represented by the following formula (1).
  • R 1 is independently an alkyl group having 1 to 20 carbon atoms (preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl), a cycloalkyl group having 3 to 20 carbon atoms (preferably cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl), aryl groups having 6 to 20 carbon atoms (preferably phenyl, naphthyl, anthranyl, phenanthryl), alkoxy groups having 1 to 20 carbon atoms (preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy) , T-butoxy), cyano group, nitro group, hydroxyl group, heterocyclic group (preferably pyridyl group, furyl group, thienyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group
  • R ′ is independently an alkyl group having 2 to 20 carbon atoms (preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, octyl, decyl, dodecyl, undecyl).
  • R ′ is independently an alkyl group having 2 to 20 carbon atoms (preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, octyl, decyl, dodecyl, undecyl).
  • R 4 is an alkyl group having 1 to 20 carbon atoms (preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl) or a cycloalkyl group having 3 to 20 carbon atoms (preferably cyclopropyl, cyclobutyl, cyclopentyl).
  • Cyclohexyl an aryl group having 6 to 20 carbon atoms (preferably phenyl, naphthyl, anthranyl, phenanthryl), an alkoxy group having 1 to 20 carbon atoms (preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t- Butoxy), cyano group, nitro group, hydroxyl group, heterocyclic group (preferably pyridyl group, furyl group, thienyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, pyrazolyl group, benzofuranyl group, morpholinyl group), halogen ( Preferably Element, chlorine, bromine, iodine), carboxyl group, or alkylsilyl group having 1 to 20 carbon atoms (preferably trimethylsilyl, triethylsilyl, tripropylsilyl, dimethylsilyl,
  • n is an integer of 0-4.
  • -LR 1 on different benzene rings may be the same or different, and when m is an integer of 2 to 4, 2 to 4 -LR 1 on the same benzene ring may be the same or different. Good.
  • Preferred examples of the trans cyclic compound represented by the above formula (1) include the following compounds.
  • R 1 , R 4 , m, and p are the same as described above.
  • the trans cyclic compound of the present invention has high heat resistance and is amorphous so that it is excellent in film forming property, does not have sublimation property, is excellent in alkali developability, etching resistance, etc., and is a resist material, particularly the main component of the resist material ( It is suitably used as a substrate.
  • various aldehydes including industrially produced aromatic aldehydes and phenols such as resorcinol and pyrogallol are subjected to a dehydration condensation reaction using a nonmetallic catalyst such as sulfuric acid, and then a column. Since it can be produced in a high yield by separation by a known method such as chromatography or preparative liquid chromatography, it is extremely excellent in practicality.
  • trans cyclic compound represented by the following formula (5-2) is more preferable.
  • trans cyclic compounds represented by the following formulas (6-1) to (6-4) are more preferable.
  • the trans cyclic compound represented by the above formula (6-3) is particularly preferable.
  • the molecular weight of the cyclic compound is 700 to 5000, preferably 800 to 2000, and more preferably 900 to 1500. Within the above range, the resolution is improved while maintaining the film formability required for the resist.
  • the radiation-sensitive composition of the present invention contains a cyclic compound mainly composed of a trans cyclic compound.
  • the cyclic compound may contain a small amount of a cis-cyclic compound.
  • the resist component of the radiation-sensitive composition has a higher uniformity of the components in the resist film, and the pattern roughness is higher when it has only the trans-cyclic compound. Since it reduces, it is more preferable. Moreover, since the sensitivity of a resist improves, it is more preferable. Accordingly, the ratio of the trans cyclic compound to the cis cyclic compound in the cyclic compound is preferably 80 to 100: 0 to 20, more preferably 90 to 100: 0 to 10, and the cyclic compound is only the trans cyclic compound. It is further preferable that it contains.
  • the cis cyclic compound is a cis isomer of the trans cyclic compound of the formula (1) and is represented by the following formula (I). (Wherein L, R 1 , R ′ and m are the same as described above.)
  • the cyclic compound having only the trans cyclic compound can be obtained by a known method such as separation by column chromatography or preparative liquid chromatography, optimization of a reaction solvent and a reaction temperature at the time of production, and the like.
  • a cyclic compound having only the trans cyclic compound represented by the above formula (1) obtains a cis-trans mixture by a condensation reaction of one or more aldehyde compounds (A1) and one or more phenol compounds (A2). It is obtained by separating the trans-cyclic compound from the mixture by a known method such as column chromatography or preparative liquid chromatography.
  • a cis-trans mixture is obtained by a condensation reaction of one or more aromatic aldehyde compounds (A1A) and one or more phenolic compounds (A2), and is obtained by a known method such as column chromatography or preparative liquid chromatography. It is obtained by separating the trans cyclic compound from the mixture.
  • the aldehyde compound (A1) has 2 to 59 carbon atoms, has 1 to 4 formyl groups, and is selected from an aromatic aldehyde compound (A1A) and an aliphatic aldehyde compound (A1B).
  • the aromatic aldehyde compound (A1A) is a benzaldehyde compound having 7 to 24 carbon atoms, such as benzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, ethylmethylbenzaldehyde, isopropylmethylbenzaldehyde, diethylbenzaldehyde, Anisaldehyde, naphthaldehyde, anthraldehyde, cyclopropylbenzaldehyde, cyclobutylbenzaldehyde, cyclopentylbenzal
  • the aromatic aldehyde compound (A1A) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired.
  • the aromatic aldehyde compound (A1A) may be used alone or in combination of two or more.
  • the aliphatic aldehyde compound (A1B) is preferably a compound having 3 to 24 carbon atoms, such as ethanal, propanal, isopropanal, butanal, isobutanal, t-butanal, pentanal, isopentanal, neopentanal, hexanal. , Isohexanal, octanal, decanal, dodecanal, undecenal, cyclopropane carboxaldehyde, cyclobutane carboxaldehyde, cyclohexane carboxaldehyde, and the like.
  • Octanal, decanal, dodecanal, cyclopropanecarboxaldehyde, cyclobutanecarboxaldehyde, cyclohexa Carboxaldehyde is preferred, octanal, decanal, dodecanal, cyclohexane carboxaldehyde more preferable.
  • the aliphatic aldehyde compound (A1B) may have a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired.
  • the aliphatic aldehyde compound (A1B) may be used alone or in combination of two or more.
  • the phenol compound (A2) preferably has 6 to 15 carbon atoms, and preferably has 1 to 3 phenolic hydroxyl groups.
  • examples of the phenol compound (A2) include phenol, catechol, resorcinol, hydroquinone, pyrogallol and the like, resorcinol and pyrogallol are preferable, and resorcinol is more preferable.
  • the phenol compound (A2) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired. You may use a phenolic compound (A2) individually or in combination of 2 or more types.
  • the trans cyclic compound represented by the above formula (1) can be produced, for example, as follows. In the presence of an acid catalyst (hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, etc.) in an organic solvent such as methanol or ethanol, 0.1 to 10 mol of phenol compound (A2) is added to 1 mol of aldehyde compound (A1). The reaction is carried out at 60 to 150 ° C. for about 0.5 to 20 hours. Next, after filtration, washing with an alcohol such as methanol, washing with water, and separation by filtration, drying is performed to obtain a crude product (cis-trans mixture).
  • an acid catalyst hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, etc.
  • organic solvent such as methanol or ethanol
  • trans cyclic compound By separating this crude product by column chromatography, preparative liquid chromatography, or the like, only the trans cyclic compound can be obtained.
  • a basic catalyst sodium hydroxide, barium hydroxide, 1,8-diazabicyclo [5.4.0] undecene-7, etc.
  • a compound is obtained.
  • the trans cyclic compound is obtained by converting the aldehyde compound (A1) into a dihalide with hydrogen halide or halogen gas, reacting the isolated dihalide with the phenol compound (A2), and then separating only the trans cyclic compound. Can also be obtained.
  • two or more aldehyde compounds (A1) and two or more phenol compounds (A2) are used.
  • the solubility of the resulting cyclic compound in a semiconductor safety solvent is improved.
  • purification may be performed as necessary. Further, if the acid catalyst and the cocatalyst remain, generally, the storage stability of the radiation sensitive composition is lowered, or if the basic catalyst remains, generally the sensitivity of the radiation sensitive composition is lowered.
  • the intended purification may be performed. Purification can be performed by a known method as long as the cyclic compound is not denatured, and is not particularly limited. For example, a method of washing with water, a method of washing with an acidic aqueous solution, a method of washing with a basic aqueous solution, or an ion exchange resin. The method of processing, the method of processing by silica gel column chromatography, etc. are mentioned.
  • Acidic aqueous solution, basic aqueous solution, ion exchange resin, and silica gel column chromatography should be optimized depending on the metal to be removed, the amount and type of acidic compound and / or basic compound, the type of cyclic compound to be purified, etc. It is possible to select appropriately.
  • Amberlyst 15J-HG Dry made by Organo can be mentioned. You may dry after refinement
  • the cyclic compound can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process.
  • the cyclic compound is useful as a negative resist material that becomes a compound that is hardly soluble in an alkali developer by irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray.
  • KrF excimer laser extreme ultraviolet light
  • electron beam or X-ray a condensation reaction between the compounds is induced and the compound becomes insoluble in an alkali developer.
  • the resist pattern thus obtained has a very low LER.
  • the cyclic compound can be used as a main component of the negative radiation-sensitive composition, and can be added to the radiation-sensitive composition as an additive for improving sensitivity and etching resistance, for example.
  • the cyclic compound is used at 1 to 49.999% by weight of the total weight of the solid component.
  • the glass transition temperature of the cyclic compound is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher.
  • the semiconductor lithography process has heat resistance capable of maintaining the pattern shape and can provide performance such as high resolution.
  • the calorific value of crystallization determined by differential scanning calorimetry of the glass transition temperature of the cyclic compound is preferably less than 20 J / g.
  • (crystallization temperature) ⁇ (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher.
  • the crystallization exotherm is less than 20 J / g, or (crystallization temperature) ⁇ (glass transition temperature) is within the above range, an amorphous film can be easily formed by spin coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.
  • the crystallization calorific value, crystallization temperature and glass transition temperature can be determined by differential scanning calorimetry using DSC / TA-50WS manufactured by Shimadzu Corporation.
  • DSC / TA-50WS manufactured by Shimadzu Corporation.
  • About 10 mg of a sample is put in an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 mL / min). After the rapid cooling, the temperature is raised again to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 mL / min). Further, after rapid cooling, the temperature is raised again to 400 ° C.
  • the temperature at the midpoint of the step difference of the baseline that has changed in a step shape is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature.
  • Tg glass transition temperature
  • the calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.
  • the cyclic compound preferably has a low sublimation property under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C. or lower, further preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower.
  • Low sublimation means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, even more preferably 1% or less, particularly preferably Is preferably 0.1% or less. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Moreover, a favorable pattern shape can be given with low LER.
  • the cyclic compound preferably satisfies M ⁇ 3.0 (M represents the total number of atoms / (total number of carbon atoms ⁇ total number of oxygen atoms)), and more preferably satisfies M ⁇ 2.5.
  • M represents the total number of atoms / (total number of carbon atoms ⁇ total number of oxygen atoms)
  • Cyclic compounds include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate
  • a solvent selected from PGMEA, PGME, and CHN and having the highest solubility for the cyclic compound is at least 20% by weight at 23 ° C., particularly preferably at least 20% by weight at 23 ° C. with respect to PGMEA. Dissolve.
  • a halogen atom may be introduced into the cyclic compound as long as the effect of the present invention is not impaired.
  • the ratio of the number of halogen atoms to the total number of constituent atoms of the cyclic compound is preferably 0.1 to 60%, more preferably 0.1 to 40%, and more preferably 0.1 to 20%. More preferably, it is 0.1 to 10%, particularly preferably 1 to 5%.
  • the film formability can be maintained while increasing the sensitivity to radiation.
  • the solubility in a safe solvent can be improved.
  • Nitrogen atoms may be introduced into the cyclic compound as long as the effects of the present invention are not impaired.
  • the ratio of the number of nitrogen atoms to the total number of constituent atoms of the cyclic compound is preferably 0.1 to 40%, more preferably 0.1 to 20%, and preferably 0.1 to 10%. Further preferred is 0.1 to 5%. Within the above range, the line edge roughness of the resulting resist pattern can be reduced.
  • the introduced nitrogen atom is preferably a secondary or tertiary nitrogen atom, and more preferably a tertiary nitrogen atom.
  • the cyclic compound is subjected to a crosslinking reaction by irradiation with visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, ion beam or chemical reaction induced thereby.
  • a crosslinkable reactive group may be introduced. The introduction is performed, for example, by reacting a cyclic compound and a crosslinking reactive group introduction reagent in the presence of a base catalyst.
  • the crosslinking reactive group include a carbon-carbon multiple bond, an epoxy group, an azide group, a halogenated phenyl group, and a chloromethyl group.
  • crosslinking reactive group introduction reagent examples include acids, acid chlorides, acid anhydrides, carboxylic acid derivatives such as dicarbonates and alkyl halides having such a crosslinking reactive group.
  • a radiation-sensitive composition containing a cyclic compound having a crosslinking reactive group is also useful as a non-polymeric radiation-sensitive composition having high resolution, high heat resistance and solvent solubility.
  • a non-acid-dissociable functional group may be introduced into at least one phenolic hydroxyl group of the cyclic compound as long as the effect of the present invention is not impaired.
  • the non-acid-dissociable functional group refers to a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group.
  • C1-20 alkyl group, C3-20 cycloalkyl group, C6-20 aryl group, C1-20 alkoxyl group, cyano group, nitro group, hydroxyl group examples thereof include a cyclic group, a halogen, a carboxyl group, a C1-20 alkylsilyl group, and a functional group selected from the group consisting of these derivatives.
  • a naphthoquinonediazide ester group may be introduced into at least one phenolic hydroxyl group of the cyclic compound as long as the effects of the present invention are not impaired.
  • a compound in which a naphthoquinone diazide ester group is introduced into at least one phenolic hydroxyl group of a cyclic compound can be used as a main component of a negative radiation sensitive composition, and can be used as a main component of a positive radiation sensitive composition, It can add to a radiation sensitive composition as an acid generator and an additive.
  • an acid-generating functional group that generates an acid upon irradiation with radiation may be introduced into at least one phenolic hydroxyl group of the cyclic compound.
  • a cyclic polyphenol compound in which an acid-generating functional group that generates an acid upon irradiation with radiation is introduced into at least one phenolic hydroxyl group of the cyclic compound can be used as a main component of a negative radiation-sensitive composition. It can be used as a main component of the radiation-sensitive composition, or can be added to the radiation-sensitive composition as an acid generator or additive.
  • the present invention relates to a radiation-sensitive composition
  • a radiation-sensitive composition comprising the above-described cyclic compound (trans cyclic compound and any cis-cyclic compound) and a solvent.
  • the radiation-sensitive composition preferably comprises 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, and the cyclic compound is 50 to 99.999% by weight of the total weight of the solid component. Is preferred.
  • the radiation-sensitive composition of the present invention can form an amorphous film by spin coating.
  • the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present invention in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. is preferably 10 ⁇ / sec or more, and preferably 10 to 10000 ⁇ . / Sec is more preferable, and 100 to 1000 kg / sec is more preferable. It can melt
  • the speed is preferably 5 K / sec or less, more preferably 0.05 to 5 K / sec, and further preferably 0.0005 to 5 K / sec. If it is 5 ⁇ / sec or less, it is insoluble in an alkali developer and can be used as a resist.
  • the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the cyclic compound is dissolved and LER is reduced. There is also an effect of reducing defects.
  • the radiation-sensitive composition of the present invention is preferably 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, more preferably 1 to 50% by weight of a solid component and 50 to 99% by weight of a solvent, and still more preferably.
  • the solid component is 2 to 40% by weight and the solvent is 60 to 98% by weight, and particularly preferably the solid component is 2 to 10% by weight and the solvent is 90 to 98% by weight.
  • the amount of the cyclic compound is arbitrarily used such as the total weight of the solid component (cyclic compound, acid generator (C), acid crosslinking agent (G), acid diffusion controller (E), and other components (F). 50 to 99.4% by weight, preferably 55 to 90% by weight, more preferably 60 to 80% by weight, and particularly preferably 60 to 70% by weight of the total of the solid components.
  • the blending ratio is as described above, high resolution is obtained and the line edge roughness is reduced.
  • the composition of the present invention generates an acid directly or indirectly by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. It is preferable to include one or more acid generators (C).
  • the amount of the acid generator used is preferably 0.001 to 49% by weight, more preferably 1 to 40% by weight, still more preferably 3 to 30% by weight, and particularly preferably 10 to 25% by weight based on the total weight of the solid components. By using within the above range, a pattern profile with high sensitivity and low edge roughness can be obtained.
  • the acid generation method is not limited as long as an acid is generated in the system.
  • excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing is possible, and if high-energy rays are used, electron beam, extreme ultraviolet rays, X-rays, ion beam, further fine processing Is possible.
  • the acid generator (C) is preferably at least one selected from the group consisting of compounds represented by the following formulas (7-1) to (7-8).
  • R 13 may be the same or different, and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. group, a hydroxyl group or a halogen atom;
  • X - is an alkyl group, an aryl group, a sulfonic acid ion or halide ion having a halogen-substituted alkyl group or halogen-substituted aryl group).
  • the compound represented by the formula (7-1) includes triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n- Octane sulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenyl Sulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethane Sulfon
  • R 14 s may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group.
  • a group, a hydroxyl group or a halogen atom, X ⁇ is the same as defined above.
  • the compound represented by the formula (7-2) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-tert-butylphenyl) iodonium, p-toluenesulfonate, bis (4-tert-butylphenyl) iodoniumbenzenesulfonate, bis (4-tert-butylphenyl) Iodonium-2-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium-2,
  • 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 (7-3) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( Trifluoromethylsulfonyloxy) 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 (10-camphorsulfonyloxy) naph
  • R 16 s may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.
  • the compound represented by the formula (7-4) is diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone. , Di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-trifluoromethylphenyl) disulfone It is preferable.
  • R 17 s may be the same or different, and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.
  • the compound represented by the formula (7-5) is ⁇ - (methylsulfonyloxyimino) -phenylacetonitrile, ⁇ - (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, ⁇ - (trifluoromethylsulfonyloxyimino).
  • 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, or cyclopentyl.
  • a cycloalkyl group such as a cyclohexyl group, an alkoxyl group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group, or an aryl group such as a phenyl group, a toluyl group, and a naphthyl group, preferably 6 carbon atoms ⁇ 10 aryl groups.
  • L 19 and L 20 are each independently an organic group having a 1,2-naphthoquinonediazide group.
  • Specific examples of the organic group having a 1,2-naphthoquinonediazide group 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.
  • p is an integer of 1 to 3
  • q is an integer of 0 to 4
  • 1 ⁇ p + q ⁇ 5 is preferable.
  • J 19 is 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 (7-7-1), a carbonyl group, an ester group, an amide group or an ether group.
  • Y 19 represents a hydrogen atom, an alkyl group or an aryl group
  • X 20 each independently represents a group represented by the following formula (7-8-1).
  • Z 22 each independently represents an alkyl group, a cycloalkyl group or an aryl group, R 22 represents an alkyl group, a cycloalkyl group or an alkoxyl group, and r represents 0-3. 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
  • acid generators having an aromatic ring are preferable, and acid generators represented by formula (7-1) or (7-2) are more preferable.
  • An acid generator having a sulfonate ion having X ⁇ in formula (7-1) or (7-2) having an aryl group or a halogen-substituted aryl group is more preferred, and an acid generator having a sulfonate ion having an aryl group are particularly preferred, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are particularly preferred.
  • LER can be reduced by using the acid generator.
  • the acid generator (C) can be used alone or in combination of two or more.
  • the radiation-sensitive composition of the present invention preferably contains one or more acid crosslinking agents (G).
  • the acid crosslinking agent (G) is a compound that can crosslink a cyclic compound within a molecule or between molecules in the presence of an acid generated from the acid generator (C).
  • Examples of such an acid crosslinking agent (G) include compounds having one or more substituents (hereinafter referred to as “crosslinkable groups”) capable of crosslinking a cyclic compound.
  • crosslinkable group examples include (i) hydroxyalkyl groups such as hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group), acetoxy (C1-C6 alkyl group) and the like.
  • substituents derived therefrom (ii) a carbonyl group such as formyl group, carboxy (C1-C6 alkyl group) or a substituent derived therefrom; (iii) a dimethylaminomethyl group, a diethylaminomethyl group, dimethylol Nitrogen-containing substituents such as aminomethyl group, diethylolaminomethyl group, morpholinomethyl group; (iv) glycidyl group-containing substituents such as glycidyl ether group, glycidyl ester group, glycidylamino group; (v) benzyloxymethyl Groups, benzoyloxymethyl groups, etc., C1-C6 allyloxy (C1-C6 Alkyl groups), substituents derived from aromatic groups such as C1-C6 aralkyloxy (C1-C6 alkyl groups); (vi) substituents containing polymerizable multiple bonds such as vinyl groups and iso
  • Examples of the acid crosslinking agent (G) having a crosslinkable substituent include (i) a methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, a methylol group-containing glycoluril compound, and a methylol group-containing phenol compound. (Ii) alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds, etc.
  • the acid crosslinking agent (G) compounds having phenolic hydroxyl groups, and compounds and resins imparted with crosslinkability by introducing the crosslinkable group into acidic functional groups in the alkali-soluble resin can be used.
  • the introduction ratio of the crosslinkable group is usually 5 to 100 mol%, preferably 10 to 60 mol%, more preferably, based on the total acidic functional group in the compound having a phenolic hydroxyl group and the alkali-soluble resin. Is adjusted to 15-40 mol%. Within the above range, the cross-linking reaction occurs sufficiently, and a decrease in the remaining film ratio, a pattern swelling phenomenon, meandering, and the like can be avoided.
  • the acid crosslinking agent (G) is preferably an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycoluril compound or a resin thereof.
  • Particularly preferred acid crosslinking agents (G) include compounds represented by the following formulas (8-1) to (8-3) and alkoxymethylated melamine compounds (acid crosslinking agent (G1)).
  • R 7 each independently represents a hydrogen atom, an alkyl group, or an acyl group
  • R 8 to R 11 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxyl group
  • X 2 represents a single bond, a methylene group, or an oxygen atom.
  • the alkyl group represented by R 7 preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the acyl group represented by R 7 preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and examples thereof include an acetyl group and a propionyl group.
  • the alkyl group represented by R 8 to R 11 preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the alkoxyl group represented by R 8 to R 11 preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group.
  • X 2 is preferably a single bond or a methylene group.
  • R 7 to R 11 and X 2 may be substituted with an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a hydroxyl group, or a halogen atom.
  • the plurality of R 7 and R 8 to R 11 may be the same or different.
  • Specific examples of the compound represented by the formula (8-2) include N, N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril.
  • N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.
  • alkoxymethylated melamine compounds include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N-hexa (ethoxymethyl) melamine N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N, N, N, N, Examples thereof include N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like.
  • the acid crosslinking agent (G1) is obtained by, for example, condensing a urea compound or a glycoluril compound, and formalin to introduce a methylol group, and then ether with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol. Then, the reaction solution is cooled and the precipitated compound or its resin is recovered.
  • the acid cross-linking agent (G1) can also be obtained as a commercial product such as CYMEL (trade name, manufactured by Mitsui Cyanamid) or Nicalac (manufactured by Sanwa Chemical Co., Ltd.).
  • the molecule has 1 to 6 benzene rings, and has at least two hydroxyalkyl groups and / or alkoxyalkyl groups in the molecule. And / or a phenol derivative in which an alkoxyalkyl group is bonded to any one of the benzene rings (acid crosslinking agent (G2)).
  • the molecular weight is 1500 or less
  • the molecule has 1 to 6 benzene rings
  • the hydroxyalkyl group and / or alkoxyalkyl group has 2 or more in total
  • the hydroxyalkyl group and / or alkoxyalkyl group is the benzene ring.
  • a phenol derivative formed by bonding to any one or a plurality of benzene rings can be given.
  • hydroxyalkyl group bonded to the benzene ring those having 1 to 6 carbon atoms such as hydroxymethyl group, 2-hydroxyethyl group, and 2-hydroxy-1-propyl group are preferable.
  • the alkoxyalkyl group bonded to the benzene ring is preferably one having 2 to 6 carbon atoms. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, 2-methoxyethyl And the 2-methoxy-1-propyl group is preferred.
  • L 1 to L 8 may be the same or different and each independently represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.
  • a phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L 1 to L 8 are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. it can.
  • the reaction temperature is preferably 60 ° C. or lower. Specifically, it can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.
  • a phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst.
  • the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like.
  • a phenol derivative having a hydroxymethyl group and / or an alkoxymethyl group synthesized in this manner is preferable in terms of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage.
  • the acid crosslinking agent (G2) may be used alone or in combination of two or more.
  • Another particularly preferable acid crosslinking agent (G) is a compound having at least one ⁇ -hydroxyisopropyl group (acid crosslinking agent (G3)).
  • the structure is not particularly limited as long as it has an ⁇ -hydroxyisopropyl group.
  • the hydrogen atom of the hydroxyl group in the ⁇ -hydroxyisopropyl group is one or more acid dissociable groups (R—COO— group, R—SO 2 — group, etc., R is a straight chain having 1 to 12 carbon atoms) From a hydrocarbon group having 3 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a 1-branched alkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms Which represents a substituent selected from the group consisting of:
  • Examples of the compound having an ⁇ -hydroxyisopropyl group include one or two types such as a substituted or unsubstituted aromatic compound, diphenyl compound, naphthalene compound, and furan compound containing at least one ⁇ -hydroxyisopropyl group.
  • benzene compound (1) a compound represented by the following general formula (9-1)
  • benzene compound (2) a compound represented by the following general formula (9-3)
  • naphthalene compound (3 a compound represented by the following general formula (9-4): And the like (hereinafter referred to as “furan compound (4)”).
  • each A 2 independently represents an ⁇ -hydroxyisopropyl group or a hydrogen atom, and at least one A 2 is an ⁇ -hydroxyisopropyl group.
  • R 51 represents a hydrogen atom, a hydroxyl group, a linear or branched alkylcarbonyl group having 2 to 6 carbon atoms, or a linear or branched structure having 2 to 6 carbon atoms. The alkoxycarbonyl group of is shown.
  • R 52 represents a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —CO—, or —COO—.
  • R 53 and R 54 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
  • benzene compound (1) examples include ⁇ -hydroxyisopropylbenzene, 1,3-bis ( ⁇ -hydroxyisopropyl) benzene, 1,4-bis ( ⁇ -hydroxyisopropyl) benzene, 1,2 ⁇ -hydroxyisopropylbenzenes such as 1,4-tris ( ⁇ -hydroxyisopropyl) benzene, 1,3,5-tris ( ⁇ -hydroxyisopropyl) benzene; 3- ⁇ -hydroxyisopropylphenol, 4- ⁇ -hydroxyisopropylphenol ⁇ -hydroxyisopropylphenols such as 3,5-bis ( ⁇ -hydroxyisopropyl) phenol and 2,4,6-tris ( ⁇ -hydroxyisopropyl) phenol; 3- ⁇ -hydroxyisopropylphenyl methyl ketone, 4- ⁇ -Hydroxyisopropyl Phenyl methyl ketone, 4- ⁇ -hydroxyisopropylphenyl ethyl ketone, 4- ⁇ -hydroxyis
  • diphenyl compound (2) examples include 3- ⁇ -hydroxyisopropylbiphenyl, 4- ⁇ -hydroxyisopropylbiphenyl, 3,5-bis ( ⁇ -hydroxyisopropyl) biphenyl, 3,3 ′.
  • naphthalene compound (3) examples include 1- ( ⁇ -hydroxyisopropyl) naphthalene, 2- ( ⁇ -hydroxyisopropyl) naphthalene, 1,3-bis ( ⁇ -hydroxyisopropyl) naphthalene, 1,4-bis ( ⁇ -hydroxyisopropyl) naphthalene, 1,5-bis ( ⁇ -hydroxyisopropyl) naphthalene, 1,6-bis ( ⁇ -hydroxyisopropyl) naphthalene, 1,7-bis ( ⁇ -hydroxyisopropyl) Naphthalene, 2,6-bis ( ⁇ -hydroxyisopropyl) naphthalene, 2,7-bis ( ⁇ -hydroxyisopropyl) naphthalene, 1,3,5-tris ( ⁇ -hydroxyisopropyl) naphthalene, 1,3,6-tris ( ⁇ -hydroxyisopropyl) naphthalene, 1,3,7-tris ( ⁇ Hydroxyisopropy
  • furan compound (4) examples include 3- ( ⁇ -hydroxyisopropyl) furan, 2-methyl-3- ( ⁇ -hydroxyisopropyl) furan, 2-methyl-4- ( ⁇ - Hydroxyisopropyl) furan, 2-ethyl-4- ( ⁇ -hydroxyisopropyl) furan, 2-n-propyl-4- ( ⁇ -hydroxyisopropyl) furan, 2-isopropyl-4- ( ⁇ -hydroxyisopropyl) furan, 2 -N-butyl-4- ( ⁇ -hydroxyisopropyl) furan, 2-t-butyl-4- ( ⁇ -hydroxyisopropyl) furan, 2-n-pentyl-4- ( ⁇ -hydroxyisopropyl) furan, 2,5 -Dimethyl-3- ( ⁇ -hydroxyisopropyl) furan, 2,5-diethyl-3- ( ⁇ -hydroxyisopropyl) fura 3,4-bis ( ⁇ -hydroxyisopropyl) furan, 2,5-dimethyl-3, 2-methyl
  • the acid crosslinking agent (G3) is preferably a compound having two or more free ⁇ -hydroxyisopropyl groups, the benzene compound (1) having two or more ⁇ -hydroxyisopropyl groups, and two or more ⁇ -hydroxyisopropyl groups. More preferably, the diphenyl compound (2) having two or more ⁇ -hydroxyisopropyl groups, and the naphthalene compound (3) having two or more ⁇ -hydroxyisopropyl groups, ⁇ -hydroxyisopropylbiphenyls having two or more ⁇ -hydroxyisopropyl groups, ⁇ -hydroxy A naphthalene compound (3) having two or more isopropyl groups is particularly preferred.
  • the acid crosslinking agent (G3) is usually obtained by a method in which a acetyl group-containing compound such as 1,3-diacetylbenzene is reacted with a Grignard reagent such as CH 3 MgBr for methylation, followed by hydrolysis. It can be obtained by a method in which an isopropyl group-containing compound such as diisopropylbenzene is oxidized with oxygen or the like to generate a peroxide and then reduced.
  • the amount of the acid crosslinking agent (G) used is preferably 0.5 to 49% by weight, more preferably 0.5 to 40% by weight, still more preferably 1 to 30% by weight, based on the total weight of the solid component. ⁇ 20% by weight is particularly preferred.
  • the blending ratio of the acid crosslinking agent (G) is 0.5% by weight or more, the effect of suppressing the solubility of the resist film in an alkaline developer is improved, the remaining film ratio is decreased, and pattern swelling and meandering are caused. Since generation
  • the blending ratio of at least one compound selected from the acid crosslinking agent (G1), the acid crosslinking agent (G2), and the acid crosslinking agent (G3) in the acid crosslinking agent (G) is not particularly limited. Various ranges can be used depending on the type of substrate used when forming the pattern.
  • the alkoxymethylated melamine compound and / or the compounds represented by (9-1) to (9-3) are 50 to 99% by weight, preferably 60 to 99% by weight, more preferably 70%. It is preferable that the amount be ⁇ 98 wt%, more preferably 80 to 97 wt%. It is preferable that the alkoxymethylated melamine compound and / or the compounds represented by (9-1) to (9-3) be 50% by weight or more of the total acid crosslinking agent component because the resolution can be improved. It is preferable to set the weight% or less because it is easy to obtain a rectangular cross-sectional shape as the pattern cross-sectional shape.
  • an acid diffusion control agent (E) having an action of controlling undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. You may mix
  • an acid diffusion controller (E) By using such an acid diffusion controller (E), the storage stability of the radiation-sensitive composition is improved. In addition, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before irradiation and the holding time after irradiation can be suppressed, and the process stability is extremely excellent.
  • Examples of such an acid diffusion controller (E) include radiolytically decomposable basic compounds such as a nitrogen atom-containing basic compound, a basic sulfonium compound, and a basic iodonium compound.
  • the acid diffusion controller can be used alone or in combination of two or more.
  • Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that are decomposed by exposure.
  • Examples of the nitrogen-containing organic compound include the following general formula (10):
  • nitrogen-containing compound (I) a diamino compound having two nitrogen atoms in the same molecule
  • nitrogen-containing compound (II) a diamino compound having two nitrogen atoms in the same molecule
  • nitrogen-containing compound (II) a diamino compound having two nitrogen atoms in the same molecule
  • nitrogen-containing compound (III) polyamino compounds and polymers having three or more
  • nitrogen-containing compound (III) polyamino compounds and polymers having three or more
  • amide group-containing compounds amide group-containing compounds
  • urea compounds urea compounds
  • nitrogen-containing heterocyclic compounds nitrogen-containing heterocyclic compounds
  • an acid diffusion control agent (E) may be used individually by 1 type, and may use 2 or more types together.
  • R 61 , R 62 and R 63 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group.
  • the alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with a hydroxyl group or the like.
  • examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and specifically include methyl groups, ethyl groups, and n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group N-ethylhexyl group, n-nonyl group, n-decyl group and the like.
  • Examples of the aryl group include those having 6 to 12 carbon atoms, and specific examples include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
  • examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an ⁇ -methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
  • nitrogen-containing compound (I) examples include mono (cyclohexanamine) such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, cyclohexylamine and the like.
  • mono (cyclohexanamine) such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, cyclohexylamine and the like.
  • Alkylamines Alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine , Methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, dicyclohexylamine and other di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n- Pentylamine, tri-n-hexylamine, tri-n-heptylamine, Tri (cyclo) alkylamines such as ri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di
  • nitrogen-containing compound (II) examples include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, Tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) ) Propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl)- 2- (4-Hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1- Chi
  • nitrogen-containing compound (III) examples include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.
  • Specific examples of the amide group-containing compound include, for example, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methylpyrrolidone.
  • urea compound examples include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri- Examples thereof include n-butylthiourea.
  • nitrogen-containing heterocyclic compound examples include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, and 2-phenylbenzimidazole; pyridine, 2-methylpyridine 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline And pyridines such as acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2. ] Octane It can be mentioned.
  • imidazoles such as imidazole, benzimidazole
  • Examples of the radiation-decomposable basic compound include the following general formula (11-1): A sulfonium compound represented by the general formula (11-2):
  • R 71 , R 72 , R 73 , R 74 and R 75 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. Represents an alkoxyl group, a hydroxyl group or a halogen atom of ⁇ 6.
  • Z ⁇ represents HO ⁇ , R—COO ⁇ (wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 11 carbon atoms, or an alkaryl group having 7 to 12 carbon atoms) or the following general formula (11-3):
  • radiolytic basic compound examples include, for example, triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenylsulfonium.
  • the blending amount of the acid diffusion controller (E) is preferably 0.001 to 49% by weight, more preferably 0.01 to 10% by weight, still more preferably 0.01 to 5% by weight, based on the total weight of the solid component. 0.01 to 3% by weight is particularly preferred. Within the above range, it is possible to prevent degradation in resolution, pattern shape, dimensional fidelity, and the like. Furthermore, even if the holding time from electron beam irradiation to heating after radiation irradiation becomes longer, the shape of the pattern upper layer portion does not deteriorate. Further, when the blending amount is 10% by weight or less, it is possible to prevent a decrease in sensitivity, developability of an unexposed portion, and the like.
  • the storage stability of the radiation-sensitive composition is improved, the resolution is improved, and the holding time before irradiation and the holding time after irradiation are reduced. Changes in the line width of the resist pattern due to fluctuations can be suppressed, and the process stability is extremely excellent.
  • the radiation-sensitive composition of the present invention includes, as necessary, other components (F) as long as the purpose of the present invention is not impaired, a dissolution accelerator, a dissolution controller, a sensitizer, a surfactant, One or more additives such as organic carboxylic acids or phosphorus oxo acids or derivatives thereof can be added.
  • Solubility Accelerator A low molecular weight solubilizer enhances the solubility of a cyclic compound during development and moderately increases the dissolution rate of the cyclic compound when the solubility of the cyclic compound in an alkali or other developer is too low. It is a component having an action, and can be used within a range not impairing the effects of the present invention.
  • the dissolution accelerator include low molecular weight phenol compounds, and examples thereof include bisphenols and tris (hydroxyphenyl) methane. These dissolution promoters can be used alone or in admixture of two or more.
  • the blending amount of the dissolution accelerator is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 49% by weight, more preferably 0 to 5% by weight, and more preferably 0 to 1% by weight based on the total weight of the solid component. Is more preferable, and 0% by weight is particularly preferable.
  • Solubility control agent is a component that acts to moderately reduce the dissolution rate during development by controlling its solubility when the cyclic compound is too soluble in an alkali or other developer. is there.
  • a dissolution control agent those that do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable.
  • 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. Can be mentioned. These 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 49% by weight, more preferably 0 to 5% by weight, and more preferably 0 to 1% by weight based on the total weight of the solid component. Is more preferable, and 0% by weight is particularly preferable.
  • Sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (C), thereby increasing the amount of acid generated, and resist. It is a component that improves the apparent sensitivity.
  • 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 appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 49% by weight, more preferably 0 to 5% by weight, and more preferably 0 to 1% by weight based on the total weight of the solid component. Is more preferable, and 0% by weight is particularly preferable.
  • the surfactant is a component having an action of improving the coating property and striation of the radiation-sensitive composition of the present invention, the developability of the resist, and the like.
  • a surfactant may be anionic, cationic, nonionic or amphoteric.
  • a preferred surfactant is a nonionic surfactant.
  • Nonionic surfactants have better affinity with the solvent used in the production of the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers and higher fatty acid diesters of polyethylene glycol, but are not particularly limited.
  • F-top (manufactured by Gemco), Mega-Fac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass), Examples include Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.)
  • the blending amount of the surfactant is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 49% by weight, more preferably 0 to 5% by weight, and more preferably 0 to 1% by weight based on the total weight of the solid component. Is more preferable, and 0% by weight is particularly preferable.
  • Organic carboxylic acid or phosphorus oxo acid or derivative thereof is further included as an optional component. Can be contained. In addition, it can be used in combination with an acid diffusion controller, or may be used alone.
  • 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 the like, and derivatives such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester or derivatives thereof, phosphinic acid such as phosphinic acid, phenylphosphinic acid and derivatives such as esters thereof. Of these, phosphonic acid is particularly preferred.
  • the organic carboxylic acid or phosphorus oxo acid or derivative thereof may be used alone or in combination of two or more.
  • the amount of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is appropriately adjusted according to the kind of the cyclic compound to be used, and is preferably 0 to 49% by weight, preferably 0 to 5% by weight based on the total weight of the solid component. More preferably, 0 to 1% by weight is further preferable, and 0% by weight is particularly preferable.
  • additives other than organic carboxylic acid or phosphorus oxo acid or derivatives thereof can be blended as necessary within a range not inhibiting the purpose.
  • additives include dyes, pigments, and adhesion aids.
  • it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced.
  • adhesion assistant because the adhesion to the substrate can be improved.
  • examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.
  • Formulation of the radiation-sensitive composition of the present invention is weight% based on solids so, Preferably 50 to 99.4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49/0 to 49, More preferably 55 to 90/1 to 40 / 0.5 to 40 / 0.01 to 10/0 to 5, More preferably 60 to 80/3 to 30/1 to 30 / 0.01 to 5/0 to 1, Particularly preferred is 60 to 70/10 to 25/2 to 20 / 0.01 to 3/0.
  • the blending ratio of each component is selected from each range so that the sum is 100% by weight. When the above composition is used, the performance such as sensitivity, resolution and alkali developability is excellent.
  • the radiation-sensitive composition of the present invention is usually prepared by dissolving each component in a solvent at the time of use to make a uniform solution, and then filtering with a filter having a pore size of about 0.2 ⁇ m, if necessary.
  • Examples of the solvent used in the preparation of the radiation-sensitive composition of the present invention include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n- Ethylene glycol monoalkyl ether acetates such as butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n- Propyl ether acetate, propylene glycol mono-n-butyl ether acetate, etc.
  • Propylene glycol monoalkyl ether acetates Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; Lactic acid such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate and n-amyl lactate Esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate
  • the radiation-sensitive composition of the present invention can contain a resin that is soluble in an alkaline aqueous solution as long as the object of the present invention is not impaired.
  • Resins that are soluble in an alkaline aqueous solution include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and heavy polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units. A combination, or a derivative thereof may be used.
  • the blending amount of the resin that is soluble in the alkaline aqueous solution is appropriately adjusted according to the type of the cyclic compound to be used, but is preferably 30 parts by weight or less, more preferably 10 parts by weight or less per 100 parts by weight of the cyclic compound. More preferably, it is 5 parts by weight or less, particularly preferably 0 part by weight.
  • the present invention relates to a method of forming a resist film on a substrate using the radiation-sensitive composition of the present invention, a step of exposing the resist film, and developing the resist film to form a resist pattern.
  • the present invention relates to a method for forming a resist pattern including a step of forming.
  • the resist pattern of the present invention can also be formed as an upper resist in a multilayer process.
  • a resist film is formed by applying the radiation-sensitive composition of the present invention on a conventionally known substrate by a coating means such as spin coating, cast coating or roll coating.
  • the conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon wafer, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. If necessary, an inorganic and / or organic film may be provided on the substrate.
  • An inorganic antireflection film is an example of the inorganic film.
  • the organic film include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.
  • the coated substrate is heated as necessary.
  • the heating conditions vary depending on the composition of the radiation sensitive composition, but are preferably 20 to 250 ° C., more preferably 20 to 150 ° C. Heating may improve the adhesion of the resist to the substrate, which is preferable.
  • the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam.
  • the exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition.
  • heating is preferably performed after irradiation with radiation.
  • the heating conditions vary depending on the composition of the radiation sensitive composition, but are preferably 20 to 250 ° C., more preferably 20 to 150 ° C.
  • a predetermined resist pattern is formed by developing the exposed resist film with an alkali developer.
  • the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline.
  • TMAH tetramethylammonium hydroxide
  • An alkaline aqueous solution in which one or more compounds are dissolved in a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used. When the concentration of the alkaline aqueous solution is 10% by mass or less, it is preferable because the exposed portion can be prevented from being dissolved in the developer.
  • an appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant can be added to the alkaline developer.
  • alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant.
  • the developing solution which consists of such alkaline aqueous solution, generally it wash
  • the pattern wiring board is obtained by etching.
  • the etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.
  • Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.
  • the residual resist pattern after etching can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development.
  • organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), etc.
  • strong alkaline aqueous solution include 1 to 20% by mass sodium hydroxide aqueous solution, A 1 to 20% by mass aqueous potassium hydroxide solution can be mentioned.
  • Examples of the peeling method include a dipping method and a spray method.
  • the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.
  • the wiring board obtained by the present invention can also be formed by a method of depositing a metal in a vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.
  • Synthesis example 1 Synthesis of CR-1 A four-necked flask (1000 mL) equipped with a well-dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, and stirring blade was placed under a nitrogen stream under resorcinol (manufactured by Kanto Chemical Co., Ltd.). 22 g, 0.2 mol), 4-isopropylbenzaldehyde (29.6 g, 0.2 mol) and dehydrated ethanol (200 mL) were added to prepare an ethanol solution. This solution was heated to 85 ° C. with a mantle heater while stirring.
  • the chemical shift value ( ⁇ ppm, TMS standard) of 1 H-NMR in deuterated dimethyl sulfoxide solvent is 1.1 to 1.3 (m, 24H), 2.6 to 2.7, 2.7 to 2 .8 (m (trans isomer), m (cis isomer), 4H), 5.5, 5.6 (s (trans isomer), s (cis isomer), 4H), 6.0 to 6.9 (m , 24H), 8.4 to 8.5 (m, 8H).
  • the compound obtained from these results was identified as the objective compound (CR-1) (yield 95%).
  • the production ratio of the trans isomer to the cis isomer was 71:29 (trans isomer: cis isomer).
  • Synthesis example 2 Synthesis of CR-2 Synthesis was performed in the same manner as in Synthesis Example 1 except that 4-isopropylbenzaldehyde was replaced with 4-cyclohexylbenzaldehyde (46.0 g, 0.2 mol) to obtain 50 g of a compound. As a result of analysis by LC-MS, this compound showed the molecular weight 1121 of the target compound.
  • the chemical shift value ( ⁇ ppm, TMS standard) of 1 H-NMR in deuterated dimethyl sulfoxide solvent is 1.2 to 1.4 (m, 20H), 1.7 to 1.9 (m, 20H), 2.2 to 2.4 (m, 4H) 5.5, 5.6 (s (trans isomer), s (cis isomer), 4H), 6.0 to 6.8 (m, 24H), 8. 4 to 8.5 (m, 8H).
  • the compound obtained from these results was identified as the objective compound (CR-1) (yield 91%).
  • the production ratio of trans isomer to cis isomer was 51:49 (trans isomer: cis isomer).
  • CR-1t CR-1 (1.5 g) was prepared by preparative HLC using ethyl acetate as a developing solvent. As a result, 0.26 g of the desired trans isomer product (hereinafter referred to as CR-1t) was obtained.
  • the chemical shift value ( ⁇ ppm, TMS standard) of 1 H-NMR in the heavy dimethyl sulfoxide solvent of the obtained compound is 1.1 to 1.2 (m, 24H), 2.6 to 2.7 (m, 4H), 5.5 (s, 4H), 6.0 (s, 2H), 6.1 (s, 2H), 6.3 (s, 2H), 6.4 (s, 2H), 6. 6, 6.6 (d, 8H), 6.8, 6.8 (d, 8H), 8.4 (s, 4H), 8.5 (s, 4H).
  • the chemical shift value ( ⁇ ppm, TMS standard) of 1 H-NMR of the obtained compound in deuterated dimethyl sulfoxide solvent is 1.2 to 1.4 (m, 20H), 1.7 to 1.8 (m, 20H), 2.2 to 2.3 (m, 4H) 5.5 (s, 4H), 6.0 (s, 2H), 6.1 (s, 2H), 6.3 (s, 2H) , 6.4 (s, 2H), 6.6, 6.6 (d, 8H), 6.7, 6.7 (d, 8H), 8.4 (s, 4H), 8.5 (s , 4H).
  • Examples 1-3 and Comparative Examples 1-2 Patterning Test After preparing the components shown in Table 1 to make a uniform solution, the mixture was filtered through a Teflon membrane filter having a pore size of 0.1 ⁇ m to prepare a radiation-sensitive composition, and the following evaluation was performed for each. The results are shown in Table 2.
  • (1) Evaluation of resolution After a resist was spin-coated on a clean silicon wafer, pre-exposure baking (PB) was performed in an oven at 110 ° C. to form a resist film having a thickness of 60 nm. The resist film was irradiated with an electron beam with a line-and-space setting of 1: 1 at 50 nm intervals using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd.).
  • ELS-7500 electron beam drawing apparatus
  • each film was heated at a predetermined temperature for 90 seconds and immersed in a 2.38 wt% TMAH aqueous solution for 60 seconds for development. Thereafter, it was washed with water for 30 seconds and dried to form a negative resist pattern. The obtained line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation). The dose amount ( ⁇ C / cm 2 ) at that time was defined as sensitivity.
  • Compound CR-2tm Mixed acid generator (C) of CR-2 and CR-2t in which the ratio of trans form to cis form is 95: 5
  • P-1 Triphenylbenzenesulfonium trifluoromethane sulfonate (Midori Chemical Co., Ltd.)
  • Acid crosslinking agent (G) C-1: Nicarak MW-100LM (Sanwa Chemical Co., Ltd.)
  • C-2 Nicalak MX-270 (Sanwa Chemical Co., Ltd.)
  • Acid diffusion controller E
  • Q-1 Trioctylamine (Tokyo Chemical Industry Co., Ltd.) Solvent
  • S-1 Cyclohexanone (Tokyo Chemical Industry Co., Ltd.)
  • S-2 Cyclopentanone (Nippon Zeon Corporation)
  • the present invention relates to a radiation-sensitive compound represented by a specific chemical structural formula, a radiation-sensitive composition containing the compound, and a resist pattern using the radiation-sensitive composition, which are useful as acid-amplified non-polymer resist materials. It is suitably used for the forming method.

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

La présente invention concerne un composé cyclique représenté par la formule (1). (Dans la formule, L, R1, R' et m sont tels que définis dans la description.) Le composé cyclique représenté par la formule (1) est très sensible et permet la formation d'une forme de motif de réserve satisfaisante, et est par conséquent utile en tant que composant pour une composition sensible au rayonnement.
PCT/JP2010/066092 2009-09-24 2010-09-16 Composé cyclique, composition sensible au rayonnement, et procédé de formation de motif de réserve WO2011037071A1 (fr)

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WO2014196425A1 (fr) * 2013-06-07 2014-12-11 三菱瓦斯化学株式会社 Composition de réserve

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US6093517A (en) * 1998-07-31 2000-07-25 International Business Machines Corporation Calixarenes for use as dissolution inhibitors in lithographic photoresist compositions
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
JP2009173623A (ja) * 2007-04-23 2009-08-06 Mitsubishi Gas Chem Co Inc 感放射線性組成物
WO2009119784A1 (fr) * 2008-03-28 2009-10-01 出光興産株式会社 Composé cyclique, processus de production d'un composé cyclique, matériau à base de résine photosensible comprenant ce composé cyclique, composition de résine photosensible, procédé de microtraitement, dispositif à semi-conducteur, et appareil
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US6093517A (en) * 1998-07-31 2000-07-25 International Business Machines Corporation Calixarenes for use as dissolution inhibitors in lithographic photoresist compositions
JP2009173623A (ja) * 2007-04-23 2009-08-06 Mitsubishi Gas Chem Co Inc 感放射線性組成物
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
WO2009119784A1 (fr) * 2008-03-28 2009-10-01 出光興産株式会社 Composé cyclique, processus de production d'un composé cyclique, matériau à base de résine photosensible comprenant ce composé cyclique, composition de résine photosensible, procédé de microtraitement, dispositif à semi-conducteur, et appareil
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014196425A1 (fr) * 2013-06-07 2014-12-11 三菱瓦斯化学株式会社 Composition de réserve
JPWO2014196425A1 (ja) * 2013-06-07 2017-02-23 三菱瓦斯化学株式会社 レジスト組成物
US9785048B2 (en) 2013-06-07 2017-10-10 Mitsubishi Gas Chemical Company, Inc. Resist composition

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