WO2015064602A1 - 積層体、有機半導体製造用キットおよび有機半導体製造用レジスト組成物 - Google Patents
積層体、有機半導体製造用キットおよび有機半導体製造用レジスト組成物 Download PDFInfo
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- WO2015064602A1 WO2015064602A1 PCT/JP2014/078698 JP2014078698W WO2015064602A1 WO 2015064602 A1 WO2015064602 A1 WO 2015064602A1 JP 2014078698 W JP2014078698 W JP 2014078698W WO 2015064602 A1 WO2015064602 A1 WO 2015064602A1
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- acid
- photoacid generator
- organic semiconductor
- organic
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- JCJNUSDBRRKQPC-UHFFFAOYSA-M tetrahexylazanium;hydroxide Chemical compound [OH-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC JCJNUSDBRRKQPC-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- H—ELECTRICITY
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/14—Semiconductor wafers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a laminate, a kit for producing an organic semiconductor, and a resist composition for producing an organic semiconductor. Specifically, in the production of an organic semiconductor, a laminate of an organic semiconductor film, a protective film and a resist film, an organic semiconductor production kit for producing such a laminate, and an organic semiconductor production used for the organic semiconductor production kit The present invention relates to a resist composition.
- Organic semiconductors have an advantage that it can be manufactured by a simple process as compared with a conventional device using an inorganic semiconductor such as silicon. Furthermore, it is possible to easily change the material characteristics by changing the molecular structure, and there are a wide variety of materials, making it possible to realize functions and elements that could not be achieved with inorganic semiconductors. It is thought to be.
- Organic semiconductors can be applied to electronic devices such as organic solar cells, organic electroluminescence displays, organic photodetectors, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, etc. There is sex. Patterning of an organic semiconductor has been performed by a printing technique so far, but there is a limit to fine processing in the patterning by the printing technique. Organic semiconductors are also susceptible to damage.
- Patent Document 1 the step of forming an organic semiconductor layer, the step of forming a protective layer for protecting the organic semiconductor layer from the mask layer on the organic semiconductor layer, and the above-mentioned having a predetermined pattern Patterning an organic semiconductor layer, comprising: forming a mask layer on the protective layer; and patterning the protective layer and further the organic semiconductor layer in the same shape by etching using the mask layer as a mask.
- the protective layer is formed of an organic polymer compound having a hydrophilic property or an insulating inorganic compound, the material being different from that of the mask layer. Yes.
- Patent Document 1 Japanese Patent Laid-Open No. 2006-413157
- Japanese Patent Laid-Open No. 2006-413157 Japanese Patent Laid-Open No. 2006-413157
- the present invention has been made to solve the above-described problem, and is a laminate capable of forming a good organic semiconductor pattern, an organic semiconductor production kit for producing such a laminate, and an organic semiconductor production It aims at providing the resist composition for organic-semiconductor manufacture used for a kit.
- the inventors have formed a protective film and a resist film made of a photosensitive resin composition in this order on one surface of the organic semiconductor film, and organic etching is performed by performing dry etching after patterning the resist film.
- the inventors have found that patterning can be performed without damaging the semiconductor, and the present invention has been completed.
- ⁇ 1> A photoacid having an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, wherein the resist film generates an organic acid having a pKa of generated acid of ⁇ 1 or less.
- a laminate comprising a photosensitive resin composition comprising a generator (A) and a resin (B) that reacts with an acid generated from the photoacid generator to reduce the dissolution rate in a developer containing an organic solvent.
- a ⁇ 2> photoacid generator (A) contains at least 1 sort (s) chosen from a sulfonic acid, a trialkyl sulfonyl methide acid, and a dialkyl sulfonyl imide acid.
- s 1 sort
- the photoacid generator (A) includes a compound having an oxime sulfonate group and / or an imide sulfonate group.
- ⁇ 4> The laminate according to ⁇ 1> or ⁇ 2>, wherein the photoacid generator (A) includes a compound having a sulfonium cation and / or an iodonium cation.
- the photoacid generator (A) includes a diazodisulfone compound and / or a disulfone compound.
- the protective film contains a water-soluble resin.
- ⁇ 7> Any one of ⁇ 1> to ⁇ 6>, wherein the photosensitive resin composition has a polarity changed by the acid generated from the photoacid generator (A), and the dissolution rate in a developer containing an organic solvent decreases.
- the laminated body as described in. ⁇ 8> The photosensitive resin composition undergoes a crosslinking reaction in the resin (B) by the acid generated from the photoacid generator (A), so that the dissolution rate in the developer containing the organic solvent is reduced.
- ⁇ 1> The laminate according to any one of ⁇ 7>.
- ⁇ 9> The laminate according to any one of ⁇ 1> to ⁇ 8>, wherein the photosensitive resin composition contains a sensitizing dye that spectrally sensitizes the photoacid generator (A).
- a kit for producing an organic semiconductor comprising a resist composition for producing an organic semiconductor comprising a resin (B) and a composition for forming a protective film comprising a water-soluble resin.
- the photoacid generator (A) includes at least one selected from sulfonic acid, trialkylsulfonylmethide acid, and dialkylsulfonylimide acid.
- ⁇ 12> The kit for producing an organic semiconductor according to ⁇ 10> or ⁇ 11>, wherein the photoacid generator (A) includes a compound having an oxime sulfonate group and / or an imide sulfonate group.
- the photoacid generator (A) includes a compound having a sulfonium cation and / or an iodonium cation.
- the photoacid generator (A) includes a diazodisulfone compound and / or a disulfone compound.
- the resist composition for manufacturing an organic semiconductor wherein the polarity is changed by an acid generated from the photoacid generator (A), and the dissolution rate in a developer containing an organic solvent is decreased.
- the kit for organic semiconductor manufacture in any one.
- the photosensitive resin composition has a crosslinking reaction in the resin (B) caused by the acid generated from the photoacid generator (A), so that the dissolution rate in a developer containing an organic solvent is reduced.
- the resist composition for producing an organic semiconductor according to ⁇ 18> wherein the photoacid generator (A) contains at least one selected from sulfonic acid, trialkylsulfonylmethide acid and dialkylsulfonylimide acid.
- the photoacid generator (A) includes a compound having an oxime sulfonate group and / or an imide sulfonate group.
- the photoacid generator (A) comprises a diazodisulfone compound and / or a disulfone compound.
- the resist composition for organic semiconductor manufacture in any one.
- the photosensitive resin composition undergoes a crosslinking reaction in the resin (B) by the acid generated from the photoacid generator (A), the dissolution rate in the developer containing the organic solvent is reduced.
- a laminate capable of forming a good organic semiconductor pattern an organic semiconductor production kit for producing such a laminate, and an organic semiconductor production resist composition for use in the organic semiconductor production kit. It became possible.
- the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- “active light” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.
- exposure in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- (meth) acrylate represents both and / or acrylate and methacrylate
- (meth) acryl represents both and / or acryl and “(meth) acrylic”
- "Acryloyl” represents both and / or acryloyl and methacryloyl.
- process is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
- the solid content concentration is the weight percentage of the weight of other components excluding the solvent with respect to the total weight of the composition. Moreover, solid content concentration says the density
- the weight average molecular weight is defined as a polystyrene converted value by GPC measurement.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgelgSuper AWM-H (manufactured by Tosoh Corporation, 6) as a column.
- the eluent was measured using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution.
- the laminate of the present invention has an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, and the resist film contains an organic acid having a generated acid pKa of ⁇ 1 or less.
- a photoacid generator (A) generated and a photosensitive resin composition containing a resin (B) that reacts with the acid generated from the photoacid generator and decreases the dissolution rate in a developer containing an organic solvent.
- an undercoat layer may be provided between the organic semiconductor film and the protective film and / or between the protective film and the resist film.
- the photosensitive resin composition in the present invention contains a photoacid generator, and the exposed portion becomes insoluble in a developer containing an organic solvent, so that a mask pattern can be formed. After forming the mask pattern, it is used as a mask for dry etching. It becomes possible to do.
- the organic semiconductor film used in the present invention is a film containing an organic material exhibiting semiconductor characteristics.
- a semiconductor made of an inorganic material there are a p-type organic semiconductor that conducts holes as carriers and an n-type organic semiconductor that conducts electrons as carriers.
- the ease of carrier flow in the organic semiconductor is represented by carrier mobility ⁇ . Although it depends on the application, in general, the mobility should be higher, preferably 10 ⁇ 7 cm 2 / Vs or more, more preferably 10 ⁇ 6 cm 2 / Vs or more, more preferably 10 ⁇ 5 cm 2 / Vs. More preferably, it is Vs or higher.
- the mobility can be obtained by characteristics when a field effect transistor (FET) element is manufactured or by a time-of-flight measurement (TOF) method.
- FET field effect transistor
- TOF time-of-flight measurement
- the organic semiconductor film is usually preferably formed on a substrate. That is, it is preferable to have a substrate on the surface of the organic semiconductor film opposite to the side where the water-soluble resin film is laminated.
- a substrate that can be used in the present invention, for example, various materials such as silicon, quartz, ceramic, polyester film such as glass polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and polyimide film may be used as the substrate.
- PEN glass polyethylene naphthalate
- PET polyethylene terephthalate
- polyimide film any substrate may be selected according to the application.
- a flexible substrate can be used in the case of use of a flexible element. Further, the thickness of the substrate is not particularly limited.
- any material of organic semiconductor material and inorganic semiconductor material may be used as long as it exhibits a hole transport property.
- a p-type ⁇ -conjugated polymer for example, substituted or substituted is used.
- Unsubstituted polythiophene eg, poly (3-hexylthiophene) (P3HT)
- polyselenophene polypyrrole
- polyparaphenylene polyparaphenylene vinylene
- polythiophene vinylene polyaniline, etc.
- condensed polycyclic compounds eg, substituted) Or unsubstituted anthracene, tetracene, pentacene, anthradithiophene, hexabenzocoronene, etc.
- triarylamine compounds eg, m-MTDATA, 2-TNATA, NPD, TPD, mCP, CBP, etc.
- hetero 5-membered ring compounds Eg substituted or unsubstituted Ligothiophene, TTF, etc.
- phthalocyanine compounds substituted or unsubstituted central metal phthalocyanine, naphthalocyanine, anthracocyanine, tetrapyraz
- any organic semiconductor material or inorganic semiconductor material may be used as long as it has a hole transporting property.
- the fullerene compound refers to a substituted or unsubstituted fullerene.
- C 60 , C 70 , C 76 , C 78 , C 80 , C 82 , C 84 , C 86 , C 88 , C 90 are used.
- C 96 , C 116 , C 180 , C 240 , C 540 and the like may be used, but substituted or unsubstituted C 60 , C 70 , C 86 are preferable, and PCBM ([6, 6] is particularly preferable.
- Electron-deficient phthalocyanines are phthalocyanines (F 16 MPc, FPc-S8, etc.), naphthalocyanines, anthracyanines, substituted or unsubstituted tetrapyrazinoporphyrazines of various central metals to which 4 or more electron withdrawing groups are bonded. Etc.
- naphthalene tetracarbonyl compound may be used, but naphthalene tetracarboxylic anhydride (NTCDA), naphthalene bisimide compound (NTCDI), and perinone pigment (Pigment Orange 43, Pigment Red 194, etc.) are preferable.
- NTCDA naphthalene tetracarboxylic anhydride
- NTCDI naphthalene bisimide compound
- perinone pigment Pigment Orange 43, Pigment Red 194, etc.
- Any perylene tetracarbonyl compound may be used, but perylene tetracarboxylic acid anhydride (PTCDA), perylene bisimide compound (PTCDI), and benzimidazole condensed ring (PV) are preferable.
- the TCNQ compound is a substituted or unsubstituted TCNQ and a compound in which the benzene ring portion of TCNQ is replaced with another aromatic ring or a heterocyclic ring, and examples thereof include TCNQ, TCAQ, TCN3T, and the like.
- graphene is also included. Particularly preferred examples of the type organic semiconductor material are shown below.
- R in the formula may be any, but is a hydrogen atom, a substituent or an unsubstituted branched or straight chain alkyl group (preferably having 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably Is preferably 1 to 8), or a substituted or unsubstituted aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms).
- Solvents include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, and 1,2-dichlorobenzene; for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, and 1,2-dichlorobenzene
- ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene and chlorotoluene; ester solvents such as ethyl acetate, butyl acetate and amyl acetate;
- alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol;
- Ether solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethyl
- polar solvents such as sulfoxide. These solvent may use only 1 type and may use 2 or more types.
- the ratio of the organic semiconductor in the composition for forming the organic semiconductor film is preferably 0.1 to 80% by mass, more preferably 0.1 to 10% by mass.
- a film having a thickness can be formed.
- the material for forming the film and the binder resin can be dissolved or dispersed in the above-mentioned appropriate solvent to form a coating solution, and the thin film can be formed by various coating methods.
- the resin binder include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, and polypropylene, and copolymers thereof.
- Photoconductive polymers such as polyvinyl carbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene.
- the resin binder may be used alone or in combination. Considering the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and considering the charge mobility, a resin binder, a photoconductive polymer, or a conductive polymer having a structure not containing a polar group is preferable.
- the blending amount is preferably 0.1 to 30% by mass in the organic semiconductor film.
- a single layer or a mixed solution containing various semiconductor materials and additives may be applied to form a blend film composed of a plurality of material types.
- a mixed solution with another semiconductor material can be used.
- the substrate may be heated or cooled, and the film quality and molecular packing in the film can be controlled by changing the temperature of the substrate.
- the temperature of the substrate is not particularly limited, but is preferably ⁇ 200 ° C. to 400 ° C., more preferably ⁇ 100 ° C. to 300 ° C., and further preferably 0 ° C. to 200 ° C.
- the characteristics of the formed organic semiconductor film can be adjusted by post-processing. For example, characteristics can be improved by changing the film morphology and molecular packing in the film by heat treatment or exposure to solvent vapor. Further, by exposing to an oxidizing or reducing gas, solvent, substance, or the like, or mixing them, an oxidation or reduction reaction can be caused to adjust the carrier density in the film.
- the thickness of the organic semiconductor film is not particularly limited and varies depending on the type of electronic device used, but is preferably 5 nm to 50 ⁇ m, more preferably 10 nm to 5 ⁇ m, and still more preferably 20 nm to 500 nm.
- the protective film of the present invention is formed on the organic semiconductor film, and is preferably formed on the surface of the organic semiconductor film. There may be an undercoat layer or the like between the organic semiconductor film and the protective film.
- the protective film is preferably one that does not damage the organic semiconductor when it is formed on the organic semiconductor, and that does not cause intermixing (interlayer mixing) when a resist film is applied on the protective film.
- the protective film is preferably a film containing a water-soluble resin, and more preferably a film containing a fat-soluble resin as a main component.
- the main component means the largest component among the components constituting the protective film, and preferably 80% by mass or more is a water-soluble resin.
- the water-soluble resin in the present invention refers to a resin having a solubility in water at 20 ° C. of 1% or more.
- the protective film is difficult to dissolve in a developer containing an organic solvent and is preferably dissolved in water. Therefore, when a water-soluble resin is used for the protective film, its sp value (solubility parameter) is preferably 18 (MPa) 1/2 or more and less than 25 (MPa) 1/2 , and 20 to 24 (MPa) The ratio is more preferably 1/2 , and further preferably 21 to 24 (MPa) 1/2 .
- the sp value is a value calculated by the Hoy method, and the Hoy method is described in POLYMER HANDBOOK FOURTH EDITION.
- the composition for protective film formation may contain 2 or more types of resin, it is preferable in this case that 2 or more types of resin each satisfy
- Water-soluble resins used in the present invention include polyvinylpyrrolidone, water-soluble polysaccharides (water-soluble cellulose (such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose), pullulan or pullulan derivatives, starch, hydroxypropyl. Starch, carboxymethyl starch, chitosan, cyclodextrin), polyvinyl alcohol, polyethylene oxide, polyethyloxazoline, and the like. Polyvinyl pyrrolidone, polyvinyl alcohol, and pullulan are preferable. Among these, polyvinyl pyrrolidone is preferable because it has a good coated surface and is easily dissolved and removed with water. Of these, two or more different main chain structures may be selected and used, or may be used as a copolymer.
- water-soluble polysaccharides water-soluble cellulose (such as methylcellulose, hydroxyethyl
- the weight average molecular weight of the resin forming the protective film used in the present invention is preferably 500 to 400,000, more preferably 2,000 to 300,000, and still more preferably 3, as a polystyrene conversion value by GPC method. 000-200,000.
- the degree of dispersion (molecular weight distribution) of the resin for the protective film is usually from 1.0 to 3.0, preferably in the range from 1.0 to 2.6.
- the protective film is formed, for example, by applying a protective film forming composition on the organic semiconductor film and drying it.
- coating is preferable.
- application methods include casting method, blade coating method, wire bar coating method, spray coating method, dipping (dipping) coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, spin coating method, The Langmuir-Blodgett (LB) method can be used.
- the solid content concentration of the composition for forming a protective film is preferably 0.5 to 30% by mass, more preferably 1.0 to 20% by mass, and 2.0 to 14% by mass. Further preferred. It can apply
- the protective film-forming composition further contains a surfactant for improving coatability.
- the surfactant may be any nonionic, anionic, or amphoteric fluorine-based one as long as it reduces the surface tension.
- examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and other polyoxyethylene alkyl ethers.
- Oxyethylene alkyl allyl ethers such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, etc.
- Sorbitan alkyl esters such as glyceride alkyl esters such as glycerol monostearate and glycerol monooleate
- Nonionic surfactants such as oligomers containing silicon or silicon, acetylene glycol, ethylene oxide adducts of acetylene glycol, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium butyl naphthalene sulfonate, sodium pentyl naphthalene sulfonate, hexyl Alkyl naphthalene sulfonates such as sodium naphthalene sulfonate and sodium octyl naphthalene sulfonate, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, s
- Anionic surfactants alkylbetaines such as lauryl betaine and stearyl betaine, and amphoteric boundaries such as amino acids
- An activator can be used, but particularly preferred is an acetylene skeleton represented by the following formula (1), which has a low content of metal ions that affect the electrical characteristics of the organic semiconductor and has excellent antifoaming properties. It has a nonionic surfactant.
- R 1 and R 2 are each independently an alkyl group having 3 to 15 carbon atoms which may have a substituent, or an aromatic carbon atom having 6 to 15 carbon atoms which may have a substituent.
- a hydrogen group or an optionally substituted heteroaromatic cyclic group having 4 to 15 carbon atoms (the substituent is an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, carbon And an aralkyl group having 7 to 17 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy-carbonyl group having 2 to 20 carbon atoms, and an acyl group having 2 to 15 carbon atoms.
- the Surfinol series manufactured by Nissin Chemical Industry Co., Ltd. is exemplified.
- the amount of the surfactant added is preferably 0.05 to 8% by mass, more preferably 0.07 to 5% by mass, when the protective film is formed. Particularly preferably, it is contained in a proportion of 0.1 to 3% by mass.
- These surfactants may be used alone or in combination of two or more.
- the protective film preferably has a thickness of 20 nm to 5 ⁇ m, and more preferably has a thickness of 100 nm to 1 ⁇ m.
- a dye may be blended in the protective film. By blending the dye, it is possible to adjust the absorption wavelength in accordance with the wavelength of the exposure light source, so that damage due to exposure of the organic semiconductor material can be effectively prevented.
- dyes As dyes, azo dyes, nitro dyes, nitrosolo dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine / polymethine dyes, thiazole dyes, indamine / indophenol dyes, azine dyes Oxazine dye, thiazine dye, sulfur dye, aminoketone dye, oxyketone dye, anthraquinone dye, indigoid dye, phthalocyanine dye and the like.
- the dye When blended, the dye may be 0.1 to 10% by mass of the protective film. The dye may be used alone or in combination.
- the photosensitive resin composition used in the present invention plays a role as a resist composition for producing an organic semiconductor, and is used for forming a resist film on a protective film.
- the photosensitive resin composition used in the present invention includes a photoacid generator (A) that generates an organic acid having a pKa of generated acid of ⁇ 1 or less, and an organic solvent that reacts with the acid generated from the photoacid generator. It contains a resin (B) whose dissolution rate in the developer is reduced.
- the first preferred embodiment of the photosensitive resin composition used in the present invention is a composition in which the polarity is changed by the organic acid generated from the photoacid generator and the dissolution rate in the developer containing the organic solvent is reduced.
- the composition has a lower dissolution rate in an organic solvent having a value of less than 19 (MPa) 1/2 , and is hardly soluble in an organic solvent having a value of 18.5 (MPa) 1/2 or less. More preferably, it is a composition, and more preferably a composition whose dissolution rate is reduced in an organic solvent of 18.0 (MPa) 1/2 or less.
- the second preferred embodiment of the photosensitive resin composition used in the present invention is a developer containing an organic solvent by causing a crosslinking reaction to occur in the resin (B) by the acid generated from the photoacid generator (A). It is a form which is a composition in which the dissolution rate for is reduced. In the present invention, an aspect satisfying both the first and second embodiments is more preferable.
- the photosensitive resin composition used in the present invention is preferably a negative resist composition because a particularly high effect can be obtained because a finer trench / hole pattern can be formed.
- the photosensitive resin composition used in the present invention contains at least a resin (B) that can be developed with a developer containing an organic solvent and a photoacid generator (A).
- the photosensitive resin composition in the present invention can form a resist film having a surface with suppressed generation of residues during development and excellent smoothness. Furthermore, the effect of this invention is exhibited more effectively by employ
- the “residue” means a residual film present at the periphery of the edge of the patterned resist film when a patterned resist film is formed using the photosensitive resin composition.
- the photoacid generator used in the present invention is a photoacid generator that generates an organic acid having a generated acid pKa of ⁇ 1 or less.
- the acid is larger than pKa-1, the reactivity of the resin (B) becomes insufficient, and the dissolution rate in a developer containing an organic solvent cannot be sufficiently reduced.
- the photoacid generator (A) when the photoacid generator (A) generates an inorganic acid, the inorganic acid diffuses into the protective film, and the pattern becomes an undercut shape or causes peeling. Furthermore, a reaction occurs between the protective film and the resin (B), which may cause a residue.
- the lower limit of pKa is not particularly defined, but is, for example, ⁇ 10 or more, preferably ⁇ 5 or more.
- the organic acid having a pKa of ⁇ 1 or less generated from the photoacid generator (A) is preferably at least one selected from sulfonic acid, trialkylsulfonylmethide acid and dialkylsulfonylimide acid.
- the photoacid generator (A) used in the present invention is: (I) a compound having an oxime sulfonate group (hereinafter also referred to as oxime sulfonate compound) and a compound having an imide sulfonate group (hereinafter also referred to as imide sulfonate group), (Ii) Compound having sulfonium cation (hereinafter also referred to as sulfonium salt) and compound having iodonium cation (hereinafter also referred to as iodonium salt) (Iii) Diazodisulfone compound and disulfone compound (more preferably, diazodisulfone compound) Those corresponding to any of the group consisting of:
- (I) Compound having oxime sulfonate group, compound having imide sulfonate group
- the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (2), formula (OS-103) described later And an oxime sulfonate compound represented by the formula (OS-104) or the formula (OS-105).
- X in Formula (2) represents an alkyl group, an alkoxy group, or a halogen atom each independently.
- the alkyl group and alkoxy group in X may have a substituent.
- the alkyl group in X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- the alkoxy group in X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
- the halogen atom in X is preferably a chlorine atom or a fluorine atom.
- M in the formula (2) represents an integer of 0 to 3, preferably 0 or 1. When m is 2 or 3, the plurality of X may be the same or different.
- R 4 in Formula (2) represents an alkyl group or an aryl group, and is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 is preferably a halogenated alkoxy group, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W.
- W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. Represents a group.
- alkyl group having 1 to 10 carbon atoms for R 4 include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tert, -Butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
- alkoxy group having 1 to 10 carbon atoms for R 4 include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyloxy group, and n-decyloxy group.
- halogenated alkyl group having 1 to 5 carbon atoms for R 4 include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro-n. -An amyl group etc. are mentioned.
- halogenated alkoxy group having 1 to 5 carbon atoms in R 4 include trifluoromethoxy group, pentafluoroethoxy group, perfluoro-n-propoxy group, perfluoro-n-butoxy group, perfluoro-n. -An amyloxy group etc. are mentioned.
- phenyl group optionally substituted with W in R 4 include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethyl.
- naphthyl group optionally substituted by W in R 4 include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl -1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group and the like.
- m is 1, X is a methyl group, the substitution position of X is an ortho position, R 4 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A compound having a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.
- Specific examples of the oxime sulfonate compound represented by the formula (2) include the following compound (i), compound (ii), compound (iii), compound (iv) and the like. May be used in combination, or two or more types may be used in combination. Compounds (i) to (iv) can be obtained as commercial products. Specific examples of the oxime sulfonate compound represented by the other formula (2) are given below.
- R 11 represents an alkyl group, an aryl group or a heteroaryl group
- a plurality of R 12 s independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom
- a plurality of R 16 independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
- X represents O or S
- n represents 1 or 2 represents m
- m represents an integer of 0 to 6.
- the alkyl group, aryl group or heteroaryl group represented by R 11 may have a substituent.
- the alkyl group represented by R 11 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
- the substituent that the alkyl group represented by R 11 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned.
- examples of the alkyl group represented by R 11 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an s-butyl group.
- the aryl group represented by R 11 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
- substituent that the aryl group represented by R 11 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples thereof include an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.
- Examples of the aryl group represented by R 11 include phenyl group, p-methylphenyl group, trimethylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group. preferable.
- the heteroaryl group represented by R 11 is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent.
- substituent that the heteroaryl group represented by R 11 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, and an aryloxycarbonyl group.
- the heteroaryl group represented by R 11 only needs to have at least one heteroaromatic ring. It may be condensed.
- the heteroaryl group represented by R 11 include a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring, which may have a substituent.
- a group obtained by removing one hydrogen atom from a ring selected from the group consisting of:
- R 12 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.
- one or two of R 12 present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
- the alkyl group or aryl group represented by R 12 may have a substituent. Examples of the substituent that the alkyl group or aryl group represented by R 12 may have include the same groups as the substituent that the alkyl group or aryl group in R 1 may have.
- the alkyl group represented by R 12 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent. It is more preferably an alkyl group having 1 to 6 carbon atoms which may have a group.
- Examples of the alkyl group represented by R 12 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, A chloromethyl group, a bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group.
- a group is more preferable, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is particularly preferable.
- the aryl group represented by R 12 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
- the aryl group represented by R 12 is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
- the halogen atom represented by R 12 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.
- X represents O or S, and is preferably O.
- the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
- n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 is preferable.
- the alkyl group and alkyloxy group represented by R 16 may have a substituent.
- the alkyl group represented by R 16 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
- the substituent that the alkyl group represented by R 16 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned.
- the alkyl group represented by R 16 is methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl.
- the alkyloxy group represented by R 16 is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.
- substituents that the alkyloxy group represented by R 16 may have include a halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl Groups.
- the alkyloxy group represented by R 16 includes a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, and a trichloromethyloxy group. Or an ethoxyethyloxy group is preferred.
- the aminosulfonyl group for R 16 include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.
- Examples of the alkoxysulfonyl group represented by R 16 include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.
- m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.
- the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), (OS-110) or (OS-111).
- the compound represented by OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108). ) Or (OS-109) is particularly preferable.
- R 11 represents an alkyl group, an aryl group or a heteroaryl group
- R 17 represents a hydrogen atom or a bromine atom
- R 18 represents a hydrogen atom
- R 19 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group
- 20 represents a hydrogen atom or a methyl group.
- R 11 in the formula (OS-106) ⁇ (OS -111) has the same meaning as R 11 in the formula (OS-103) ⁇ (OS -105), preferable embodiments thereof are also the same.
- R 17 in the above formula (OS-106) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
- R 18 in the above formulas (OS-106) to (OS-111) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or Represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferred is a methyl group.
- R 19 in the above formulas (OS-108) and (OS-109) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
- R 20 in the above formulas (OS-108) to (OS-111) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
- the oxime steric structure (E, Z) may be either one or a mixture.
- oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include the following exemplified compounds, but the present invention is not limited thereto.
- oxime sulfonate compound having at least one oxime sulfonate group is a compound represented by the following formula (OS-101).
- R 11 is a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, aryl group or heteroaryl group Represents.
- R 12 represents an alkyl group or an aryl group.
- X is -O -, - S -, - NH -, - NR 15 -, - CH 2 -, - CR 16 H- or -CR 16 R 17 - represents, in each of R 15 ⁇ R 17 independently represent an alkyl Represents a group or an aryl group.
- R 21 to R 24 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group or aryl. Represents a group. Two of R 21 to R 24 may be bonded to each other to form a ring. R 21 to R 24 are preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R 21 to R 24 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 21 to R 24 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the above-described substituents may further have a substituent.
- the compound represented by the above formula (OS-101) is more preferably a compound represented by the following formula (OS-102).
- R 11, R 12 and R 21 ⁇ R 24 has the same meaning as R 11, R 12 and R 21 ⁇ R 24 in each formula (OS-101), preferred examples also It is the same.
- R 11 in the formula (OS-101) and the formula (OS-102) is a cyano group or an aryl group is more preferable, represented by the formula (OS-102), in which R 11 is a cyano group, phenyl
- the embodiment which is a group or a naphthyl group is most preferred.
- the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
- b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.
- Commercially available products include WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-443 (structure below, manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (structure below, manufactured by Midori Chemical Co., Ltd.) Etc.
- Examples of the imidosulfonate compound include compounds represented by general formula (ZV).
- R 208 represents an alkyl group or an aryl group.
- A represents an alkylene group, an alkenylene group or an arylene group.
- a ring may be formed via a carbonyl group.
- the alkyl group for R 208 is preferably a linear alkyl group or a cyclic alkyl group.
- R 208 is preferably a linear or branched alkyl group or an aryl group. These groups may be substituted or unsubstituted.
- a ring may be formed via a carbonyl group, and the cyclic alkyl group may be polycyclic.
- it is a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group or pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group). Or a norbornyl group).
- the alkyl group for R 208 may be further substituted with, for example, a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and / or a nitro group.
- the aryl group for R 208 is preferably a phenyl group or a naphthyl group.
- R 20 8 Noariru groups are, for example, a halogen atom, an alkoxy group (e.g. having 1 to 5 carbon atoms), a hydroxyl group, a cyano group and / or further by a nitro group may be substituted, but is preferably a C1-10 A linear or branched alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group or pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group or norbornyl group). Can be mentioned.
- the alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 carbon atoms.
- alkenylene groups eg, ethenylene group, propenylene group, butenylene group, etc.
- arylene groups having 6 to 10 carbon atoms eg, phenylene group, tolylene group, naphthylene group, etc.
- a naphthylene group is a preferable example when i-line is used as an exposure wavelength.
- sulfonium salt, iodonium salt sulfonium salt or iodonium salt has an anion which is non-nucleophilic and photodecomposes an organic acid having a pKa of ⁇ 1 or less.
- R 201 , R 202 and R 203 each independently represents an organic group.
- the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Further, two members out of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
- Z ⁇ represents a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion, etc.), Examples include a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methide anion.
- the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.
- the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
- the alkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms).
- an alkylthio group preferably having 1 to 15 carbon atoms
- an alkylsulfonyl group preferably having 1 to 15 carbon atoms
- an alkyliminosulfonyl group preferably having 1 to 15 carbon atoms
- an aryloxysulfonyl group preferably having carbon atoms Number 6 to 20
- alkylaryloxysulfonyl group preferably having 7 to 20 carbon atoms
- cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like.
- examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
- aralkyl group in the aralkyl carboxylate anion preferably an aralkyl group having 7 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like can be mentioned.
- Examples of the sulfonylimide anion include saccharin anion.
- the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
- substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like.
- a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
- the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
- Z ⁇ represents a carbon number in the cation from the viewpoint of suppressing intermixing (mixing of sulfonium salt and iodonium salt into the protective film) when the photosensitive resin composition is applied on the protective film layer. It preferably contains an aromatic ring group having three or more alkyl groups as substituents.
- the alkyl group preferably has 6 or more carbon atoms, more preferably 8 or more.
- the alkyl group may be linear, branched or cyclic, and specifically includes n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-amyl, i-amyl. , Tert-amyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, n-octyl, 2-ethylhexyl, and the like.
- the anion is preferably a sulfonate containing an alkyl group having 6 or more carbon atoms or a sulfonate containing an aromatic ring having an alkyl group having 3 or more carbon atoms as a substituent.
- Z ⁇ is particularly preferably an anion represented by the following general formula (AN1).
- Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R 1 and R 2 , R 1 and R 2 may be the same or different.
- L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
- A represents a cyclic organic group.
- x represents an integer of 0 to 20
- y represents an integer of 0 to 10
- z represents an integer of 0 to 10.
- the alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
- the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
- Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
- Xf include a fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , and CH 2 CH 2 C 4 F 9 are mentioned, among which a fluorine atom and CF 3 are preferable. In particular, it is preferable that both Xf are fluorine atoms.
- the alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent for R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , and C 7 F 15.
- R 1 and R 2 are preferably a fluorine atom or CF 3 .
- x is preferably 0 to 10, more preferably 0 to 2.
- y is preferably from 0 to 8, and more preferably from 0 to 6.
- z is preferably 0 to 5, and more preferably 0 to 3.
- the divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred.
- —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.
- the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
- the alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group.
- a polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred.
- an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.
- Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
- Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.
- examples of the cyclic organic group may include a lactone structure, and specific examples include those represented by the general formulas (LC1-1) to (LC1-17) that may be included in the resin (A). Can be mentioned.
- the cyclic organic group may have a substituent, and the substituent may be a linear or branched alkyl group (which may be linear, branched or cyclic, and has 1 to 12 carbon atoms. ), A cycloalkyl group (which may be monocyclic, polycyclic or spirocyclic, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group or an alkoxy group. Ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like.
- the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.
- Examples of the organic group for R 201 , R 202 and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
- R 201 , R 202 and R 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
- aryl group in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.
- Preferred examples of the alkyl group and cycloalkyl group represented by R 201 to R 203 include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- These groups may further have a substituent.
- substituents include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.
- the structure is preferably a structure represented by the following general formula (A1).
- R 1a to R 13a each independently represents a hydrogen atom or a substituent. Of R 1a to R 13a , 1 to 3 are preferably not hydrogen atoms, and more preferably any one of R 9a to R 13a is not a hydrogen atom. Za is a single bond or a divalent linking group. X ⁇ has the same meaning as Z ⁇ in formula (ZI).
- R 1a to R 13a are not hydrogen atoms include halogen atoms, linear, branched, and cyclic alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, nitro groups, and carboxyl groups.
- Examples of the divalent linking group for Za include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether bond, a thioether bond, an amino group, a disulfide group, and — (CH 2 ) N —CO—, — (CH 2 ) n —SO 2 —, —CH ⁇ CH—, aminocarbonylamino group, aminosulfonylamino group and the like (n is an integer of 1 to 3).
- Preferred structures when at least one of R 201 , R 202 and R 203 is not an aryl group include paragraphs 0046 to 0048 of JP-A-2004-233661 and paragraphs 0040 to 0040 of JP-A-2003-35948.
- R 204 to R 205 each represents an aryl group.
- the aryl group for R 204 to R 205 is the same as the aryl group described as the aryl group for R 201 to R 203 in the aforementioned compound (ZI).
- the aryl group of R 204 to R 205 may have a substituent. Examples of this substituent include those that the aryl group of R 201 to R 203 in the above-mentioned compound (ZI) may have.
- Diazodisulfone compound disulfone compound
- Examples of the diazodisulfone compound include compounds represented by the following general formula (ZIII).
- R 206 to R 207 each independently represents an aryl group or an alkyl group.
- the aryl group and alkyl group of R 206 to R 207 are the same as the aryl group and alkyl group described as the aryl group and alkyl group of R 201 to R 203 in the aforementioned compound (ZI).
- the aryl group and alkyl group of R 206 to R 207 may have a substituent. Examples of this substituent include those that the aryl group and alkyl group of R 201 to R 203 in the aforementioned compound (ZI) may have.
- Examples of the disulfone compound include compounds represented by the following general formula (ZIV).
- Ar 3 and Ar 4 each independently represents an aryl group.
- Specific examples of the aryl group of Ar 3 and Ar 4 include the same examples as the specific examples of the aryl group as R 201 , R 202 and R 203 in the general formula (ZI).
- the photosensitive resin composition in the present invention preferably does not contain a 1,2-quinonediazide compound as an acid generator sensitive to actinic rays.
- a 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is 1 or less.
- a photoacid generator that generates an acid generated in response to actinic rays and a resin whose decomposition is accelerated by the action of an acid or a resin whose crosslinking is promoted by the action of an acid. High sensitivity is obtained by using it.
- the acid generator of the present invention may be used alone or in combination of two or more.
- the acid generator is preferably used in an amount of 0.1 to 20% by weight, preferably 0.5 to 18% by weight, based on the total solid content of the photosensitive resin composition. It is more preferable.
- the resin (B) used in the present invention is a resin containing a repeating unit having a group (hereinafter also referred to as “acid-decomposable group”) protected by a leaving group that decomposes and leaves by the action of an acid.
- (B-1) and / or a resin (B-2) containing a repeating unit having a crosslink between the molecular chains of the resin (B) due to the action of an acid (hereinafter also referred to as “crosslinkable group”) Preferably there is.
- a resin (B-3) that forms a crosslinked structure between resins by a crosslinking agent.
- the resin (B-1) By using the resin (B-1), it is possible to obtain a composition in which the polarity is changed by the organic acid generated from the photoacid generator and the dissolution rate in the developer containing the organic solvent is reduced. ), A crosslinking reaction occurs in the resin (B) by the acid generated from the photoacid generator (A), whereby a composition in which the dissolution rate in the developer containing the organic solvent is reduced can be obtained.
- a resin combining the resin (B-1) and the resin (B-2) is also preferable.
- the polar group generated by the decomposition of an acid-decomposable group by the action of an acid is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent, but is acidic such as a carboxyl group or a sulfonic acid group.
- Groups groups conventionally dissociated in a 2.38% by mass tetramethylammonium hydroxide aqueous solution used as a resist developer), hydroxyl groups (alcoholic hydroxyl groups, phenolic hydroxyl groups, etc.) and the like.
- the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group).
- An aliphatic alcohol substituted with an attractive group for example, a fluorinated alcohol group (such as hexafluoroisopropanol group) is excluded.
- the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.
- a preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
- Examples of the group capable of leaving with an acid include -C (R 36 ) (R 37 ) (R 38 ), -C (R 36 ) (R 37 ) (OR 39 ), -C (R 01 ) (R 02 ). ) (OR 39 ) and the like.
- R 36 to R 39 each independently represents an alkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 36 and R 37 may be bonded to each other to form a ring.
- the alkyl group is a linear, branched or cyclic alkyl group.
- R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an alkenyl group.
- the linear or branched alkyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- A butyl group, a hexyl group, an octyl group, etc. can be mentioned.
- the cycloalkyl group of R 36 to R 39 , R 01 and R 02 may be monocyclic or polycyclic.
- the monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- the polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms.
- at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
- the aryl group of R 36 to R 39 , R 01 and R 02 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
- the aralkyl group of R 36 to R 39 , R 01 and R 02 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.
- the alkenyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
- the ring formed by combining R 36 and R 37 is preferably a cycloalkyl group (monocyclic or polycyclic).
- the cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.
- a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.
- the repeating unit having an acid-decomposable group contained in the resin (B-1) is preferably a repeating unit represented by the following general formula (III).
- R 0 represents a hydrogen atom or a linear or branched alkyl group.
- R 1 to R 3 each independently represents a linear or branched alkyl group, or a monocyclic or polycyclic cycloalkyl group. Two of R 1 to R 3 may combine to form a monocyclic or polycyclic cycloalkyl group.
- the linear or branched alkyl group for R 0 may have a substituent, and is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, n- Examples include propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like.
- the substituent include a hydroxyl group and a halogen atom (for example, a fluorine atom).
- R 0 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
- the alkyl group for R 1 to R 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group.
- Examples of the cycloalkyl group represented by R 1 to R 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.
- Examples of the cycloalkyl group formed by combining two of R 1 to R 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group
- a monocyclic cycloalkyl group such as a group is preferred.
- a monocyclic cycloalkyl group having 5 or 6 carbon atoms is particularly preferred.
- R 1 is a methyl group or an ethyl group
- R 2 and R 3 are bonded to form the above-described cycloalkyl group
- Each of the above groups may have a substituent.
- the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group (1 to 4 carbon atoms), a cycloalkyl group (3 carbon atoms).
- alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (2 to 6 carbon atoms), and the like, and those having 8 or less carbon atoms are preferred.
- R 1 , R 2 and R 3 each independently represents a linear or branched alkyl group.
- the linear or branched alkyl group for R 1 , R 2 and R 3 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group. Group, n-butyl group, isobutyl group and tert-butyl group.
- R 1 is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
- R 2 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
- R 3 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group, more preferably a methyl group, an ethyl group, an isopropyl group or an isobutyl group.
- a group, an ethyl group and an isopropyl group are particularly preferred.
- Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
- Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms.
- Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other.
- p represents 0 or a positive integer.
- Specific examples and preferred examples of Z are the same as specific examples and preferred examples of the substituent that each group such as R 1 to R 3 may have.
- the repeating unit having an acid-decomposable group is a repeating unit having a group in which a carboxy group or a phenolic hydroxyl group is protected with an acetal, or a group in which a carboxy group or a phenolic hydroxyl group is protected with a ketal. It is also preferable.
- the acid-decomposable group is preferably a group in which a carboxy group is protected with an acetal or ketal represented by the following general formula (a1-1).
- the carboxy group is a residue protected with an acetal or ketal represented by the following general formula (a1-1)
- the residue as a whole is — (C ⁇ O) —O—CR 1 R 2 (OR 3 ) structure.
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group, provided that, .R 3 except in the case of R 1 and R 2 are both hydrogen atoms, Represents an alkyl group, and R 1 or R 2 and R 3 may be linked to form a cyclic ether.
- R 1 to R 3 each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic.
- both R 1 and R 2 do not represent a hydrogen atom, and at least one of R 1 and R 2 represents an alkyl group.
- R 1 , R 2 and R 3 represent an alkyl group
- the alkyl group may be linear, branched or cyclic.
- the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
- the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
- Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
- the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
- R 1 , R 2 and R 3 When it has a halogen atom as a substituent, R 1 , R 2 and R 3 become a haloalkyl group, and when it has an aryl group as a substituent, R 1 , R 2 and R 3 become an aralkyl group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
- the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group.
- the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
- the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is a linear group.
- it when it is a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
- R 1 , R 2 and R 3 represent an aryl group
- the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable.
- the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.
- R 1 , R 2 and R 3 can be bonded to each other to form a ring together with the carbon atom to which they are bonded.
- Examples of the ring structure when R 1 and R 2 , R 1 and R 3 or R 2 and R 3 are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
- either one of R 1 and R 2 is preferably a hydrogen atom or a methyl group.
- R represents a hydrogen atom or a methyl group.
- the repeating unit having an acid-decomposable group used in the present invention is also preferably a repeating unit represented by the following general formula (XP).
- General formula (XP) (In the general formula (XP), R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group, and R 3 represents Represents an alkyl group or an aryl group, R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents an arylene group.
- R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R 1 and R 2 are aryl groups, a phenyl group is preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. X is preferably a phenylene group. Although the example of the repeating unit represented by general formula (XP) is shown below, it cannot be overemphasized that this invention is not limited to these.
- XP general formula
- the repeating unit having an acid-decomposable group in the resin (B-1) may be one type, or two or more types may be used in combination.
- the content (preferably the repeating unit represented by the above general formula (III)) having an acid-decomposable group is the total content (when including plural types)
- the total repeating unit in the resin (B-1) It is preferably 20 to 90% by mole or more, more preferably 30 to 80% by mole, particularly preferably 40 to 70% by mole, and most preferably 40 to 60% by mole.
- Resin (B-1) may contain other repeating units in addition to the repeating unit having an acid-decomposable group.
- Other repeating units include a repeating unit represented by general formula (I), a repeating unit having a non-phenolic aromatic group other than the repeating unit represented by general formula (I), and a repeating unit having a lactone structure. Examples thereof include a repeating unit having an acid group, a repeating unit having a hydroxyl group and / or a cyano group, and a repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability.
- Xa represents a hydrogen atom or a linear or branched alkyl group.
- Rx represents a hydrogen atom or a group capable of decomposing and leaving by the action of an acid.
- linear or branched alkyl group for Xa are the same as those described above as specific examples and preferred examples of the linear or branched alkyl group for R 0 in formula (III). Is mentioned.
- Specific examples and preferred examples of the group that decomposes and leaves by the action of an acid for Rx include a group that decomposes and removes by the action of an acid protecting the polar group constituting the acid-decomposable group in the resin (B-1).
- Specific examples and preferred examples of the releasing group include the same as those described above.
- the content of the repeating unit represented by the general formula (B-1) (the total when there are a plurality of types) is the solubility in the organic developer in the exposed area. From the viewpoint of sufficiently reducing the solubility of the unexposed area while improving the dissolution contrast while being sufficiently reduced, it is preferably 30 mol% or less with respect to all repeating units in the resin (B-1). It is more preferably 10 mol% or less, further preferably 5 mol% or less, ideally 0 mol%, that is, it is particularly preferable that the repeating unit is not contained. When the repeating unit represented by the general formula (I) is present in an amount of 30 mol% or more with respect to all the repeating units in the resin (B-1), it is too soluble in the organic solvent and the pattern resolution and rectangularity Tend not to be obtained.
- the resin (B-1) preferably has a repeating unit having a non-phenolic aromatic group other than the repeating unit represented by the general formula (I).
- a repeating unit having a non-phenolic aromatic group other than the repeating unit represented by the above general formula (I) means a phenolic hydroxyl group such as the repeating unit represented by the above general formula (I).
- a repeating unit having an aromatic group having an aromatic group having a group derived from a phenolic hydroxyl group for example, a group protected by a group in which the phenolic hydroxyl group is decomposed and eliminated by the action of an acid
- the repeating unit which has an aromatic group which does not have phenolic hydroxyl groups other than a unit is said.
- the non-phenolic aromatic group may have a substituent and is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
- the substituent is not particularly limited as long as it is not a phenolic hydroxyl group, and is a linear or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a 6 to 10 carbon atoms. Examples thereof include an aryl group, a halogen atom such as a fluorine atom, a cyano group, an amino group, a nitro group, and a carboxyl group.
- the linear or branched alkyl group having 1 to 4 carbon atoms, the cycloalkyl group having 3 to 10 carbon atoms, and the aryl group having 6 to 10 carbon atoms as the substituent may further have a substituent.
- such additional substituents include halogen atoms such as fluorine atoms.
- the non-phenolic aromatic group is a phenyl group and the phenyl group has a substituent
- the substituent is preferably substituted at the 4-position of the phenyl group.
- the non-phenolic aromatic group is preferably a phenyl group which may have a substituent from the viewpoint of etching resistance.
- the repeating unit having a non-phenolic aromatic group other than the repeating unit represented by the general formula (I) is preferably a repeating unit represented by the following general formula (II).
- R 01 represents a hydrogen atom or a linear or branched alkyl group.
- X represents a single bond or a divalent linking group.
- Ar represents a non-phenolic aromatic group.
- R 4 represents a single bond or an alkylene group.
- linear or branched alkyl group for R 01 are the same as those described above as specific examples and preferred examples of the linear or branched alkyl group for R 0 in formula (III). Things.
- X is preferably a divalent linking group.
- Preferred examples of the divalent linking group include —COO— and —CONH—.
- Specific examples and preferred examples of the non-phenolic aromatic group Ar include those described above as specific examples and preferred examples of the non-phenolic aromatic group.
- the alkylene group for R 4 may have a substituent and is preferably an alkylene group having 1 to 4 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group.
- Examples of the substituent that the alkylene group for R 4 may have include an alkyl group having 1 to 4 carbon atoms and a halogen atom such as a fluorine atom.
- the substituent that the alkylene group for R 4 may have and the substituent that the non-phenolic aromatic group Ar may bond may form a ring, and the group that forms the ring includes alkylene A group (for example, ethylene group, propylene group) can be mentioned.
- R 4 is preferably a single bond or a methylene group which may be substituted with a substituent from the viewpoint of a suitable glass transition temperature (Tg) of the resin in pattern formation.
- the content (preferably the repeating unit represented by the general formula (II)) of the repeating unit having the non-phenolic aromatic group is the sum of the repeating units.
- the resin (B-1) may further have a repeating unit having a lactone structure.
- the repeating unit having a lactone structure is more preferably a repeating unit represented by the following general formula (AII).
- Rb 0 represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms). Preferred substituents that the alkyl group represented by Rb 0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
- Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these.
- Ab is preferably a single bond or a divalent linking group represented by —Ab 1 —CO 2 —.
- Ab 1 is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
- V represents a group having a lactone structure.
- any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure.
- Those in which other ring structures are condensed in the form to be formed are preferred.
- the lactone structure may be directly bonded to the main chain.
- Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), (LC1-14).
- the lactone structure moiety may or may not have a substituent (Rb 2 ).
- Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 2 to 8 carbon atoms. , Carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group.
- n 2 represents an integer of 0 to 4. When n 2 is 2 or more, the plural substituents (Rb 2 ) may be the same or different, and the plural substituents (Rb 2 ) may be bonded to form a ring. .
- the repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used.
- One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
- the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
- the resin (B-1) may or may not contain a repeating unit having a lactone structure, but when it contains a repeating unit having a lactone structure, the content of the repeating unit in the resin (B-1) Is preferably in the range of 0.5 to 50 mol%, more preferably in the range of 1 to 40 mol%, and still more preferably in the range of 3 to 30 mol% with respect to all repeating units.
- One repeating unit may be used, or two or more repeating units may be used in combination.
- the resolution of the pattern is improved and the rectangular profile is improved.
- Specific examples of the repeating unit having a lactone structure in the resin (B-1) are shown below, but the present invention is not limited thereto.
- Rx represents H, CH 3 , CH 2 OH or CF 3 .
- the resin (B-1) may have a repeating unit having an acid group.
- the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the ⁇ -position, and has a carboxyl group. It is more preferable to have a repeating unit. By including a repeating unit having an acid group, the resolution in contact hole applications and the like is increased.
- the repeating unit having an acid group includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acid group in the main chain of the resin through a linking group.
- a repeating unit that is bonded, or a polymerization initiator or chain transfer agent having an acid group is introduced at the end of the polymer chain at the time of polymerization is preferred, and the linking group is a monocyclic or polycyclic cyclic hydrocarbon structure You may have.
- Particularly preferred are repeating units of acrylic acid or methacrylic acid.
- Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.
- Rx represents H, CH 3 , CH 2 OH, or CF 3 .
- the resin (B-1) may or may not contain a repeating unit having an acid group, but when the resin (B-1) contains a repeating unit having an acid group, the content of the repeating unit is as follows: The content is preferably 1 to 25 mol%, more preferably 1 to 20 mol%, still more preferably 3 to 15 mol%, based on all repeating units in the resin (A).
- the resin (B-1) may have a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility.
- the repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having a hydrocarbon structure substituted with a hydroxyl group or a cyano group.
- the hydrocarbon structure is preferably a linear, branched or cyclic aliphatic hydrocarbon group, and more preferably a repeating unit having an alicyclic hydrocarbon structure.
- the repeating unit which has a hydroxyl group and / or a cyano group does not have an acid-decomposable group.
- the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably different from the repeating unit having an acid-decomposable group (that is, it is a stable repeating unit with respect to an acid). preferable).
- the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
- More preferred examples include repeating units represented by any of the following general formulas (AIIa) to (AIIc).
- R X represents a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group.
- Ab represents a single bond or a divalent linking group. Examples of the divalent linking group represented by Ab include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof.
- the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group.
- Ab is preferably a single bond or an alkylene group.
- Rp represents a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group.
- a plurality of Rp may be the same or different, but at least one of the plurality of Rp represents a hydroxyl group or a hydroxyalkyl group.
- the resin (B-1) may or may not contain a repeating unit having a hydroxyl group or a cyano group, but the resin (B-1) contains a repeating unit having a hydroxyl group or a cyano group.
- the content of the repeating unit having a hydroxyl group or a cyano group is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, still more preferably 5 with respect to all repeating units in the resin (B-1). ⁇ 25 mol%.
- Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.
- the resin (B-1) in the present invention can further have a repeating unit which has a hydrocarbon structure having no polar group (for example, the above acid group, hydroxyl group and cyano group) and does not exhibit acid decomposability.
- a repeating unit which has a hydrocarbon structure having no polar group (for example, the above acid group, hydroxyl group and cyano group) and does not exhibit acid decomposability.
- the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent.
- Examples of such a repeating unit include a repeating unit represented by the general formula (IV).
- R 5 represents a hydrocarbon group having no polar group.
- Ra represents a hydrogen atom, an alkyl group or a —CH 2 —O—Ra 2 group.
- Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
- Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
- the hydrocarbon group having no polar group of R 5 is preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group, an ethyl group, or an n-propyl group.
- substituents examples include a nitro group, a halogen atom such as a fluorine atom, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 6 carbon atoms). 14), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), and the like. Is not to be done.
- the hydrocarbon group not having the polar group of R 5 may have a cyclic structure.
- the cyclic structure includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
- the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group.
- a preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferred examples include a cyclopentyl group and a cyclohexyl group.
- the polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group.
- the bridged cyclic hydrocarbon ring for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.)
- Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [4.3.1.1 2,5 ] undecane ring, tetracyclo [ 4.4.0.1 2,5 .
- the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene.
- a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.
- Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.
- These alicyclic hydrocarbon groups may have a substituent.
- Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done.
- Preferred halogen atoms include bromine, chlorine, and fluorine atoms
- preferred alkyl groups include methyl, ethyl, butyl, and tert-butyl groups.
- the above alkyl group may further have a substituent, and examples of the substituent which may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The group can be mentioned.
- Examples of the hydrogen atom substituent include an alkyl group (including a cycloalkyl group), an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group.
- Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups.
- acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.
- the resin (B-1) has a hydrocarbon structure having no polar group and may or may not contain a repeating unit that does not exhibit acid decomposability, but the resin (B-1) has a polar group.
- the content of the repeating unit is 1 to 49 mol% to 40 mol with respect to all the repeating units in the resin (B-1). %, More preferably 1 to 20 mol%.
- Specific examples of the repeating unit having a hydrocarbon structure not having a polar group and not exhibiting acid decomposability are listed below, but the present invention is not limited thereto.
- Ra represents H, CH 3 , CH 2 OH, or CF 3 .
- Resin (B-2) is a resin (B-2a) containing a repeating unit having a group (hereinafter also referred to as “crosslinkable group”) that causes crosslinking between the molecular chains of resin (B) by the action of an acid.
- resin (B-2b) in which crosslinking is formed between the molecular chains of the resin (B) through a crosslinking agent.
- the crosslinking group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment in the presence of an acid.
- the repeating unit having a crosslinking group at least one selected from the group consisting of an epoxy group, an oxetanyl group, —NH—CH 2 —OR (R is an alkyl group having 1 to 20 carbon atoms) and a vinyl ether group.
- the repeating unit containing is mentioned.
- the component (A) preferably contains a repeating unit containing at least one of an epoxy group and an oxetanyl group, and contains a repeating unit containing an oxetanyl group. Is particularly preferred. In more detail, the following are mentioned.
- the (A) copolymer preferably includes a repeating unit having an epoxy group and / or an oxetanyl group.
- the 3-membered cyclic ether group is also called an epoxy group, and the 4-membered cyclic ether group is also called an oxetanyl group.
- the above repeating group having an epoxy group and / or oxetanyl group is preferable, and a repeating unit having an oxetanyl group is more preferable.
- the above repeating having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one repeating unit, one or more epoxy groups and one or more oxetanyl groups, It may have the above epoxy group or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups. It is more preferable to have one or two groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.
- radical polymerizable monomer used for forming the repeating unit having an epoxy group examples include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
- radical polymerizable monomer used for forming the repeating unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. An acid ester etc. can be mentioned.
- Specific examples of the radical polymerizable monomer used for forming the repeating group having the epoxy group and / or oxetanyl group are preferably a monomer having a methacrylic ester structure and a monomer having an acrylic ester structure. .
- a (meth) acrylic acid ester having an oxetanyl group particularly preferred is a (meth) acrylic acid ester having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953.
- glycidyl methacrylate 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetane-3-yl) methacrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl
- methacrylic acid 3-ethyloxetane-3-yl
- acrylic acid (3-ethyloxetane-3-yl) methyl
- methacrylic acid 3-ethyloxetane-3-yl) methyl.
- R represents a hydrogen atom or a methyl group.
- an oxetanyl group is preferable from the viewpoint of sensitivity.
- alicyclic epoxy groups and oxetanyl groups are preferred.
- an epoxy group and / or an oxetanyl group an alicyclic epoxy group and an oxetanyl group are preferable, and an oxetanyl group is especially preferable.
- the copolymer used in the present invention is also preferably a repeating unit having —NH—CH 2 —O—R (R is an alkyl group having 1 to 20 carbon atoms). Accordingly, a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained.
- R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
- the repeating unit is more preferably a repeating unit having a group represented by the following general formula (1).
- General formula (1) (In the above formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 20 carbon atoms.) R 2 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
- R 2 examples include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.
- the copolymer used in the present invention is also preferably a repeating unit having a vinyl ether group.
- the repeating unit represented by the following general formula is given as an example.
- Ra represents a hydrogen atom, an alkyl group, or a —CH 2 —O—Ra 2 group.
- Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
- Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
- Rve is a group having a vinyl ether group at the end, and specifically, a 2- (vinyloxy) alkyl group is preferable.
- the alkyl group is preferably an alkyl group having 2 to 6 carbon atoms, and among them, a 2- (vinyloxy) ethyl group is preferred.
- the total number of repeating units of the resin (B-2a) is preferably 3 to 70 mol%, more preferably 10 to 60 mol%, containing a crosslinkable group.
- the resin (B-2b) includes a repeating unit that reacts with the crosslinking agent described below to form a bond.
- other repeating units include a repeating unit represented by the general formula (I) and a repeating unit having a non-phenolic aromatic group other than the repeating unit represented by the general formula (I).
- These can be referred to the description of the resin (B-1), and preferred ranges are also synonymous.
- a resin containing a repeating unit having a benzene ring and / or a phenolic hydroxyl group is preferable.
- a resin include a repeating unit represented by the above general formula (I), wherein Rx is a hydrogen atom, and non-phenol other than the repeating unit represented by the above general formula (I)
- An example is a repeating unit having an aromatic group, and Ar is a phenyl group.
- it may have other repeating units described above (repeating units having a crosslinkable group, repeating units having an acid-decomposable group, etc., particularly repeating units having an acid-decomposable group).
- the number of repeating units having a benzene ring and / or a phenolic hydroxyl group is preferably 50 to 100 mol% of all repeating units.
- the resin (B) used in the composition of the present invention has, in addition to the above repeating units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics of the photosensitive resin composition. It is possible to have various repeating structural units for the purpose of adjusting the resolution, heat resistance, sensitivity, and the like.
- Such a repeating structural unit include, but are not limited to, repeating units corresponding to the following monomers.
- performance required for the resin used for the photosensitive resin composition in the present invention in particular, (1) Solubility in coating solvent, (2) Film formability (glass transition point), (3) Alkali developability, (4) Film thickness reduction (selection of hydrophilicity / hydrophobicity, alkali-soluble group), (5) Adhesion of unexposed part to substrate, (6) Fine adjustment such as dry etching resistance can be performed.
- addition polymerization selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic esters, and the like. Examples include compounds having one unsaturated bond.
- any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating units may be copolymerized.
- the content molar ratio of each repeating unit is the dry etching resistance of the photosensitive resin composition, the standard developer suitability, the substrate adhesion, the resist profile, Is appropriately set in order to adjust the general required performance of the resist, such as resolution, heat resistance, and sensitivity.
- the form of the resin (B) in the present invention may be any of random type, block type, comb type, and star type.
- Resin (B) can be synthesized, for example, by radical, cation, or anionic polymerization of unsaturated monomers corresponding to each structure. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
- the resin (B) in the present invention can be synthesized according to a conventional method (for example, radical polymerization).
- a conventional method for example, radical polymerization
- a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
- the dropping polymerization method is added, and the dropping polymerization method is preferable.
- reaction solvent examples include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
- a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
- azo initiator an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
- Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like.
- an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery.
- the concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
- the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
- Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less.
- Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent
- a normal method such as a method can be applied.
- the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.
- the solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the above-mentioned polymer.
- hydrocarbon, halogenated hydrocarbon, nitro A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use.
- the amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally, 100 to 10,000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300 to 1000 parts by mass.
- the temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.).
- the precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
- the precipitated or re-precipitated polymer is usually subjected to common solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. The drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure). In addition, after depositing and separating the resin once, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent.
- a solvent in which the polymer is hardly soluble or insoluble is contacted to precipitate a resin (step a)
- the resin is separated from the solution (step b), and dissolved again in the solvent to obtain a resin solution A.
- Step c the resin solution A is brought into contact with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less).
- This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
- the synthesized resin is dissolved in a solvent to form a solution.
- a step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.
- the weight average molecular weight of the resin (B) used in the composition of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, more preferably in terms of polystyrene by GPC method. More preferably, it is 3,000 to 70,000, particularly preferably 5,000 to 50,000.
- the weight average molecular weight By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
- the degree of dispersion is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.2 to 2.4, and particularly preferably 1.4 to 2.2. Those in the range are used. When the molecular weight distribution satisfies the above range, the resolution and resist shape are excellent, the side wall of the resist pattern is smooth, and the roughness is excellent.
- the blending ratio of the resin (A) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content. It is.
- the resin (B) may be used alone or in combination.
- the photosensitive resin composition used in the present invention may contain a crosslinking agent.
- the cross-linking agent is not limited as long as it undergoes a cross-linking reaction by heat treatment in the presence of an acid.
- a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, or a compound having at least one ethylenically unsaturated double bond can be added. .
- these crosslinking agents compounds having two or more epoxy groups or oxetanyl groups in the molecule are preferable, and epoxy resins are particularly preferable.
- the addition amount of the crosslinking agent in the photosensitive resin composition used in the present invention is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive resin composition, preferably 0.5 to The amount is more preferably 30 parts by weight, and further preferably 2 to 10 parts by weight. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. Only one type of cross-linking agent may be used, or two or more types may be used in combination. When two or more types of cross-linking agents are used in combination, the content of all the cross-linking agents is calculated.
- JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051
- bisphenol F-type epoxy resins such as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Co., Ltd.), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.)
- the phenol novolac type epoxy resin JER152, JER154, JER157S70, JER157S65 (manufactured by Japan Epoxy Resin Co.,
- ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX- 832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX- 14L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-201,
- bisphenol A type epoxy resins bisphenol F type epoxy resins, phenol novolac type epoxy resins, aliphatic epoxies, and aliphatic epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferable.
- a specific example is YX-4000H manufactured by Mitsubishi Chemical Corporation.
- Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX above, manufactured by Toagosei Co., Ltd.
- Alkoxymethyl group-containing crosslinking agent preferably contains a compound having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule.
- Preferred crosslinking agents include hydroxymethylated or alkoxymethylated phenolic compounds, alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds and alkoxymethylated urea compounds, among which hydroxymethylated or alkoxymethylated compounds.
- a phenolic phenol compound is more preferable because a good pattern shape can be obtained.
- a particularly preferred compound (C) as a crosslinking agent a phenol derivative containing 3 to 5 benzene rings in the molecule, having two or more hydroxymethyl groups or alkoxymethyl groups, and having a molecular weight of 1200 or less, And melamine-formaldehyde derivatives and alkoxymethylglycoluril derivatives having at least two free N-alkoxymethyl groups.
- the actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains at least two compounds having two or more alkoxymethyl groups in the molecule as a crosslinking agent from the viewpoint of pattern shape. It is more preferable that at least two phenol compounds having 2 or more in the molecule are included, and at least one of the at least two phenol compounds includes 3 to 5 benzene rings in the molecule, and further alkoxymethyl Particularly preferred is a phenol derivative having two or more groups in total and having a molecular weight of 1200 or less. As the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable.
- a phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound not having a hydroxymethyl group with formaldehyde under a base catalyst.
- 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.
- a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of sensitivity and storage stability.
- Examples of other preferred crosslinking agents include alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively.
- the type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of outgas generated, A methoxymethyl group is preferred.
- alkoxymethyl group-containing crosslinking agents are available as commercial products.
- Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 manufactured by Mitsui Cyanamid Co., Ltd.
- Nicalack MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicalack MS-11, Nicarak MW-30HM, -100LM, -390 (above, manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.
- Examples of such compounds include hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl glycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethylene urea, bismethoxymethyl urea, and the like.
- 133, 216A West German Patent No. 3,634,671, No. 3,711,264, EP 0,212,482A. Particularly preferred among these crosslinking agents are listed below.
- L 1 to L 8 each independently represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group or an alkyl group having 1 to 6 carbon atoms.
- the crosslinking agent is used in an amount of preferably 3 to 65% by mass, more preferably 5 to 50% by mass in the solid content of the actinic ray-sensitive or radiation-sensitive composition.
- the photosensitive resin composition used in the present invention can contain a sensitizing dye in order to promote its decomposition in combination with (B) the photoacid generator.
- a sensitizing dye in order to promote its decomposition in combination with (B) the photoacid generator.
- it is preferably used when at least one of a compound having a sulfonium cation, a compound having an iodonium cation, a diazodisulfone compound and a disulfone compound is used.
- a sensitizing dye absorbs actinic rays or radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
- a photo-acid generator raise
- preferable sensitizing dyes include compounds belonging to the following compounds and having an absorption wavelength in any of 350 nm to 450 nm.
- Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
- xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
- xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
- cyanines eg, thiacarbocyanine, oxacarbocyanine
- merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
- sensitizing dyes polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
- polynuclear aromatics anthracene derivatives are most preferred. Only one kind of sensitizing dye may be used, or two or more kinds thereof may be used. When using 2 or more types, the total amount becomes the said range.
- the blending amount of the sensitizing dye is preferably 0.1 to 20% by mass of the photoacid generator, and more preferably 1 to 10% by mass.
- the photosensitive resin composition in the present invention preferably contains a solvent.
- the photosensitive resin composition in the present invention is preferably prepared as a solution in which optional components of the specific resin and the specific photoacid generator, which are essential components, and various additives are dissolved in a solvent.
- solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl.
- Ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like.
- Examples of the solvent used in the photosensitive resin composition in the present invention include (1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether.
- ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether.
- ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether; (3) ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene Ethylene glycol monoalkyl ethers such as glycol monobutyl ether acetate Acetates; (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; (5) propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl Propylene glycol dialkyl ethers such as ether and diethylene glycol monoethyl ether;
- Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; (7) diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl Diethylene glycol dialkyl ethers such as methyl ether; (8) diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, etc.
- Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
- Dipropylene glycol dimethyl ether Dipropylene glycol dialkyl ethers such as dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;
- Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate; (12) methyl lactate, lactic acid Lactic acid esters such as ethyl, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, N-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl prop
- Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
- N-methylformamide, N, N-dimethyl examples include amides such as formamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and (17) lactones such as ⁇ -butyrolactone.
- propylene glycol monoalkyl ether acetates and / or diethylene glycol dialkyl ethers are preferable, and diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are particularly preferable.
- These solvents can be used alone or in combination of two or more.
- the content of the solvent is preferably 1 to 3,000 parts by weight per 100 parts by weight of the resin (B), and is 5 to 2,000 parts by weight. More preferred is 10 to 1,500 parts by weight. Only one type of solvent may be used, or two or more types of solvents may be used. When two or more types are used, the total amount falls within the above range.
- the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
- aliphatic amines examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
- aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
- heterocyclic amine examples include, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine and 4-photosensitive resin composition of the present invention.
- a basic compound is included.
- the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
- aliphatic amines examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
- aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
- heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexylmorpholinoethylthiourea, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3 .0] Such as 7-undecene and the like
- Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
- Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
- the basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. It is preferable to use two kinds of heterocyclic amines in combination.
- the content of the basic compound is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the specific resin, and 0.002 to More preferably, it is 0.2 parts by weight.
- the photosensitive resin composition used by this invention contains surfactant from a viewpoint of improving applicability
- the surfactant any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
- nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and silicone surfactants. .
- the photosensitive resin composition in the present invention more preferably contains a fluorine-based surfactant and / or a silicone-based surfactant as the surfactant.
- fluorosurfactants and silicone surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, Surfactants described in JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 are listed. Commercially available surfactants can also be used.
- Examples of commercially available surfactants that can be used include EFTOP EF301, EF303 (above, Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, PolyFox series (OMNOVA) such as F176, F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PF-6320, etc. Fluorine-based surfactants or silicone-based surfactants, etc.). Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.
- a surfactant it contains a structural unit A and a structural unit B represented by the following formula (1), and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
- a preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.
- R 1 and R 3 each independently represent a hydrogen atom or a methyl group
- R 2 represents a linear alkylene group having 1 to 4 carbon atoms
- R 4 represents a hydrogen atom or carbon number
- 1 represents an alkyl group having 1 to 4 carbon atoms
- L represents an alkylene group having 3 to 6 carbon atoms
- p and q are weight percentages representing a polymerization ratio
- p is a numerical value of 10% to 80% by weight.
- Q represents a numerical value of 20 wt% or more and 90 wt% or less
- r represents an integer of 1 or more and 18 or less
- n represents an integer of 1 or more and 10 or less.
- L is preferably a branched alkylene group represented by the following formula (2).
- R 5 in Formula (2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. More preferred is an alkyl group of 3.
- the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
- These surfactants can be used individually by 1 type or in mixture of 2 or more types.
- the addition amount of the surfactant is preferably 10 parts by weight or less, and 0.01 to 10 parts by weight with respect to 100 parts by weight of the specific resin. More preferred is 0.01 to 1 part by weight.
- the photosensitive resin composition of the present invention includes an antioxidant, a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, an ultraviolet absorber, a thickener, and an organic material.
- an antioxidant e.g., an antioxidant, a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, an ultraviolet absorber, a thickener, and an organic material.
- well-known additives such as an inorganic precipitation inhibitor, can be added. Details of these can be referred to the descriptions in paragraph numbers 0143 to 0148 of JP2011-209692A, the contents of which are incorporated herein.
- the thickness of the resist film is preferably 100 to 1000 nm, more preferably 300 to 850 nm, from the viewpoint of improving resolution.
- Such a film thickness can be obtained by setting the solid content concentration in the photosensitive resin composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
- the patterning method of the organic semiconductor film in the present invention is: (1) forming a protective film on the organic semiconductor film; (2) forming a resist film made of a photosensitive resin composition containing a photoacid generator that generates an organic acid having a pKa of ⁇ 1 or less on the opposite side of the protective film to the organic semiconductor film; (3) a step of exposing the resist film; (4) a step of developing using a developer containing an organic solvent to produce a mask pattern; (5) a step of removing at least the non-mask portion of the protective film and the organic semiconductor film by dry etching treatment; (6) a step of dissolving the protective film with water; It is characterized by including.
- the organic semiconductor film patterning method of the present invention includes a step of forming a protective film on the organic semiconductor film. Usually, this process is performed after forming an organic semiconductor film on a substrate. In this case, the protective film is formed on the surface opposite to the surface of the organic semiconductor on the substrate side.
- the protective film is usually provided on the surface of the organic semiconductor film, but other layers may be provided without departing from the spirit of the present invention. Specific examples include a water-soluble undercoat layer. Further, only one protective film may be provided, or two or more protective films may be provided.
- a resist film made of a photosensitive resin composition is formed on the side of the protective film opposite to the surface on the organic semiconductor side.
- the resist film is preferably formed by applying a photosensitive resin composition to the surface of the protective film, but may be interposed through a film such as an undercoat layer.
- the description of the protective film can be referred to for the method of applying the photosensitive resin composition.
- the solid content concentration of the photosensitive resin composition is usually 1.0 to 20% by mass, preferably 1.5 to 17% by mass, and more preferably 2.0 to 15% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the water-soluble resin film, and further, a resist pattern having a high resolution and a rectangular profile can be formed. .
- the solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the resin composition.
- PEB post-exposure heating step
- a low-pressure mercury lamp For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, or the like can be used.
- actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used.
- Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.
- 343 nm and 355 nm are preferably used for a solid (YAG) laser
- 351 nm (XeF) is preferably used for an excimer laser
- 375 nm and 405 nm are preferably used for a semiconductor laser.
- 355 nm and 405 nm are more preferable from the viewpoints of stability and cost.
- the coating can be irradiated with the laser once or a plurality of times.
- the energy density per pulse of the laser is preferably 0.1 mJ / cm 2 or more and 10,000 mJ / cm 2 or less. In order to sufficiently cure the coating film, 0.3 mJ / cm 2 or more is more preferable, and 0.5 mJ / cm 2 or more is most preferable. To prevent the coating film from being decomposed by an ablation phenomenon, 1,000 mJ / cm 2 is preferable. cm 2 or less is more preferable, and 100 mJ / cm 2 or less is most preferable.
- the pulse width is preferably 0.1 nsec or more and 30,000 nsec or less.
- the frequency of the laser is preferably 1 Hz to 50,000 Hz, more preferably 10 Hz to 1,000 Hz. Furthermore, the frequency of the laser is more preferably 10 Hz or more, most preferably 100 Hz or more for shortening the exposure processing time, and more preferably 10,000 Hz or less for improving the alignment accuracy during the scan exposure. 000 Hz or less is most preferable.
- a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
- the exposure apparatus There are no particular restrictions on the exposure apparatus that can be used in the present invention.
- Commercially available exposure apparatuses include Callisto (manufactured by Buoy Technology), AEGIS (manufactured by Buoy Technology), and DF2200G (Dainippon). Screen Manufacturing Co., Ltd.) can be used. Further, devices other than those described above are also preferably used.
- irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
- polar solvents such as ketone solvents, ester solvents, amide solvents, and hydrocarbon solvents
- ketone solvent examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Examples include methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
- ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl.
- amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
- hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
- aromatic hydrocarbon solvents such as toluene and xylene
- aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
- the above solvents may be used alone or in combination of two or more. Moreover, you may mix and use with solvents other than the above.
- the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
- substantially as used herein means, for example, that the water content of the entire developing solution is 3% by mass or less, and more preferably the measurement limit or less.
- the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
- the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents and amide solvents.
- the organic developer may contain an appropriate amount of a basic compound as required. As an example of a basic compound, what was mentioned above in the term of a basic compound can be mentioned.
- the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
- Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, formate , Ester solvents
- Examples thereof include aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents such as octane and decane.
- Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone.
- Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate, N-methyl-2-pyrrole Emissions, N, N- dimethylacetamide, N, N-dimethylformamide amide solvents, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.
- aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.
- an appropriate amount of a surfactant can be added to the developer as necessary.
- surfactant described in the column of the said water-soluble resin composition is used preferably.
- the amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0%, based on the total amount of the developer. 0.5% by mass.
- a development method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
- dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
- paddle a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time
- spray method a method of spraying the developer on the substrate surface
- the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is preferably 2mL / sec / mm 2 or less, more preferably 1.5mL / sec / mm 2 or less, more preferably 1mL / sec / mm 2 or less.
- the flow rate 0.2 mL / sec / mm 2 or more is preferable in consideration of throughput.
- the details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
- the developer discharge pressure (mL / sec / mm 2 ) is a value at the developing nozzle outlet in the developing device.
- Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
- a step of stopping development may be performed while substituting with another solvent.
- Step of removing at least protective film and organic semiconductor of non-mask part by dry etching process The resist film is developed to produce a mask pattern, and at least the water-soluble resin film and the organic semiconductor in the non-mask portion are removed by etching.
- a non-mask part represents the location which is not exposed by the mask at the time of producing a mask pattern by exposing a resist film.
- the dry etching at least the protective film and the organic semiconductor are dry etched using the resist pattern as an etching mask.
- Representative examples of dry etching include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, and the like. There is a method described in this publication.
- the dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle and reducing damage to the organic semiconductor.
- a mixed gas of fluorine-based gas and oxygen gas (O 2 ) the first stage etching is performed to the region (depth) where the organic semiconductor is not exposed, and after this first stage etching, nitrogen gas ( N 2) and using a mixed gas of oxygen gas (O 2), over-etching preferably performed and the etching of the second step of performing etching to the vicinity area (depth) to expose the organic semiconductor, after the organic semiconductor is exposed
- N 2 nitrogen gas
- O 2 a mixed gas of oxygen gas
- Dry etching is performed by obtaining etching conditions in advance by the following method.
- (1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
- (2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
- (3) The first stage etching is performed according to the etching time calculated in (2) above.
- the second stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
- Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.
- the mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O 2 ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape.
- the first step etching process can avoid damage to the organic semiconductor by performing etching to a region where the organic semiconductor is not exposed.
- the second etching step and the over-etching step may be performed by etching the organic semiconductor to a region where the organic semiconductor is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first etching step, and then damaging the organic semiconductor. From the viewpoint of avoidance, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.
- the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable.
- the etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.
- the etching preferably includes an over-etching process.
- the overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first.
- the over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.
- a solvent or water water is preferred.
- the method for removing the water-soluble resin film with water include a method for removing the protective film by spraying cleaning water onto the resist pattern from a spray-type or shower-type spray nozzle.
- pure water can be preferably used.
- the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support.
- the resist pattern can be more effectively moved by spraying cleaning water by moving from the center of the support to the end of the support at least twice during the process of removing the water-soluble resin film. Can be removed. It is also preferable to perform a process such as drying after removing water.
- the drying temperature is preferably 80 to 120 ° C.
- an electronic device is a device that contains a semiconductor and has two or more electrodes, and the current flowing between the electrodes and the generated voltage are controlled by electricity, light, magnetism, chemical substances, or the like. It is a device that generates light, electric field, magnetic field, etc. by the applied voltage or current.
- Examples include organic photoelectric conversion elements, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, and the like.
- the organic photoelectric conversion element can be used for both optical sensor applications and energy conversion applications (solar cells). Among these, an organic field effect transistor, an organic photoelectric conversion element, and an organic electroluminescence element are preferable, an organic field effect transistor and an organic photoelectric conversion element are more preferable, and an organic field effect transistor is particularly preferable.
- each compound represents the following compound, respectively.
- THPMA 2-tetrahydropyranyl methacrylate (synthetic product)
- V-601 2,2-azobis (2-methylpropionic acid) dimethyl (manufactured by Wako Pure Chemical Industries, Ltd.)
- PGMEA Methoxypropyl acetate (manufactured by Daicel Chemical Industries, Ltd.)
- the obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), and triethylamine (1.5 g) and 2,4,6-triisopropylphenylsulfonyl chloride (3.8 g) were added under ice-cooling. The temperature was raised to 1 hour and reacted for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain a photoacid generator A1 (2.3 g).
- the reaction mixture was cooled to room temperature, ethyl acetate (300 ml) was added, and the resulting precipitate was removed by filtration.
- Isopropanol (30 ml) and 1N hydrochloric acid (10 ml) were added to a place where the reaction solution was separated and washed with deionized water, heated at 60 ° C. for 3 hours, cooled to room temperature, and crystallized in 1 L of distilled water.
- the obtained crystal was dissolved in a mixed solution of THF (100 ml) and IPA (30 ml), and a salt solution was then added by adding a THF solution of di (4-t-butylphenyl) iodonium bromide (3.5 g).
- X1 Polyvinylpyrrolidone (Pitzkor K-30, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
- X2 Polyvinyl alcohol (PXP-05, manufactured by Nippon Vinegar Poval Co., Ltd.)
- X3 Pullulan (Made by Hayashibara)
- X4 Methylcellulose (Metroise SM-4, Shin-Etsu Chemical Co., Ltd.)
- Y1 Surfynol 440 (manufactured by Nissin Chemical Industry Co., Ltd.)
- Mw 19000 B6 Monomer unit weight ratio (60/20/20)
- Mw 19000 B7 Monomer unit weight ratio (60/30/10)
- Mw 24000 B8 Monomer unit weight ratio (30/60/10)
- Mw 10,000 B9 Monomer unit weight ratio (40/50/10)
- Mw 11000 B10 Monomer unit weight ratio (50/35/15)
- Mw 11000 B11 Mw3000
- ⁇ Formation of protective film on organic semiconductor film> As an organic semiconductor, 10 mL of a P3HT (Merck) chlorobenzene solution having a concentration of 20 g / L and 10 mL of a [60] PCBM (Solenne) chlorobenzene solution having a concentration of 14 g / L are mixed, and a spin coater (on a 4-inch bare silicon substrate). The coating was performed at 1200 rpm for 30 seconds and dried on a hot plate at 140 ° C. for 15 minutes to form an organic semiconductor film having a thickness of 100 nm. A wafer having an organic semiconductor film formed on a substrate was designated as wafer 1.
- the photosensitive resin composition shown in the following Table 1 is applied to the 4-inch wafer 2 described above by a spin coater (1200 rpm, 30 seconds), and then baked at 110 ° C. for 60 seconds to form a resist having a thickness of 500 nm on the wafer 2.
- a wafer 3 on which a film was formed was formed.
- the wafer 3 is exposed with an i-line projection exposure apparatus NSR2005i9C (manufactured by Nikon Corporation) under the optical conditions of NA: 0.57 and sigma: 0.60 (exposure 120 mJ / cm 2 ), and the line width is 10 ⁇ m. Exposure was through a binary mask with a 1: 1 line and space pattern.
- the film was heated at 110 ° C. for 60 seconds, developed with butyl acetate for 15 seconds, and spin-dried to obtain a 1: 1 line and space resist pattern having a line width of 10 ⁇ m.
- rectangular profile C the bottom portion of the photosensitive resin composition has an undercut of 0.5 ⁇ m or less, and the taper angle of the pattern is in the range of 95 ° to 105 ° (reverse taper).
- D Pattern shape is poor or no pattern is formed.
- the substrate obtained is washed with water, the pattern made of the protective film is removed, and then heated at 100 ° C. for 10 minutes to remove moisture remaining in the organic semiconductor 1 and to repair the damage in the process by drying. A substrate with a patterned film was obtained.
- the line width of the organic semiconductor was evaluated by observing the pattern of the organic semiconductor after dry etching and removal of the protective film using a scanning electron microscope.
- C The line width of the organic semiconductor under the 1 ⁇ m L / S pattern of the photosensitive resin composition Less than 8 ⁇ m
- the laminated body of this invention is excellent in a resist pattern shape, and is a technique useful for fine pattern formation of an organic semiconductor. Moreover, about the line
- the display device described in FIG. 2 of JP2012-216501A can be easily manufactured.
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Abstract
Description
有機半導体のパターニングは、これまで印刷技術により行われてきたが、印刷技術によるパターニングでは微細加工に限界がある。また、有機半導体はダメージを受けやすい。
本発明は、上記問題を解決するためになされたものであり、良好な有機半導体パターンを形成可能な積層体およびかかる積層体を製造するための、有機半導体製造用キット、ならびに、有機半導体製造用キットに用いる有機半導体製造用レジスト組成物を提供することを目的とする。
<1>有機半導体膜と、上記有機半導体膜上の保護膜と、上記保護膜上のレジスト膜を有し、上記レジスト膜が、発生酸のpKaが-1以下の有機酸を発生する光酸発生剤(A)と、上記光酸発生剤から生じる酸に反応して有機溶剤を含む現像液に対する溶解速度が減少する樹脂(B)を含む感光性樹脂組成物からなる積層体。
<2>光酸発生剤(A)が、スルホン酸、トリアルキルスルホニルメチド酸およびジアルキルスルホニルイミド酸から選ばれる少なくとも1種を含む、<1>に記載の積層体。
<3>光酸発生剤(A)が、オキシムスルホネート基および/またはイミドスルホネート基を有する化合物を含む、<1>または<2>に記載の積層体。
<4>光酸発生剤(A)が、スルホニウムカチオンおよび/またはヨードニウムカチオンを有する化合物を含む、<1>または<2>に記載の積層体。
<5>光酸発生剤(A)が、ジアゾジスルホン化合物および/またはジスルホン化合物を含む、<1>または<2>に記載の積層体。
<6>保護膜が水溶性樹脂を含む、<1>~<5>のいずれかに記載の積層体。
<7>感光性樹脂組成物が、光酸発生剤(A)から生じる発生酸によって極性が変化し、有機溶剤を含む現像液に対する溶解速度が減少する、<1>~<6>のいずれかに記載の積層体。
<8>感光性樹脂組成物が、光酸発生剤(A)から生じる発生酸によって樹脂(B)に架橋反応が起こることで、有機溶剤を含む現像液に対する溶解速度が減少する、<1>~<7>のいずれかに記載の積層体。
<9>感光性樹脂組成物が、光酸発生剤(A)を分光増感する増感色素を含む、<1>~<8>のいずれかに記載の積層体。
<10>発生酸のpKaが-1以下の有機酸を発生する光酸発生剤(A)と、上記光酸発生剤から生じる酸に反応して有機溶剤を含む現像液に対する溶解速度が減少する樹脂(B)を含む、有機半導体製造用レジスト組成物と、水溶性樹脂を含む保護膜形成用組成物を含む、有機半導体製造用キット。
<11>光酸発生剤(A)が、スルホン酸、トリアルキルスルホニルメチド酸およびジアルキルスルホニルイミド酸から選ばれる少なくとも1種を含む、<10>に記載の有機半導体製造用キット。
<12>光酸発生剤(A)が、オキシムスルホネート基および/またはイミドスルホネート基を有する化合物を含む、<10>または<11>に記載の有機半導体製造用キット。
<13>光酸発生剤(A)が、スルホニウムカチオンおよび/またはヨードニウムカチオンを有する化合物を含む、<10>または<11>に記載の有機半導体製造用キット。
<14>光酸発生剤(A)が、ジアゾジスルホン化合物および/またはジスルホン化合物を含む、<10>または<11>に記載の有機半導体製造用キット。
<15>上記有機半導体製造用レジスト組成物が、光酸発生剤(A)から生じる酸によって極性が変化し、有機溶剤を含む現像液に対する溶解速度が減少する、<10>~<14>のいずれかに記載の有機半導体製造用キット。
<16>感光性樹脂組成物が、光酸発生剤(A)から生じる酸によって樹脂(B)に架橋反応が起こることで、有機溶剤を含む現像液に対する溶解速度が減少する、<10>~<15>のいずれかに記載の有機半導体製造用キット。
<17>さらに、光酸発生剤(A)を分光増感する増感色素を含む、<10>~<16>のいずれかに記載の有機半導体製造用キット。
<18>発生酸のpKaが-1以下の有機酸を発生する光酸発生剤(A)と、上記光酸発生剤から生じる酸に反応して有機溶剤を含む現像液に対する溶解速度が減少する樹脂(B)を含む、有機半導体製造用レジスト組成物。
<19>光酸発生剤(A)が、スルホン酸、トリアルキルスルホニルメチド酸およびジアルキルスルホニルイミド酸から選ばれる少なくとも1種を含む、<18>に記載の有機半導体製造用レジスト組成物。
<20>光酸発生剤(A)が、オキシムスルホネート基および/またはイミドスルホネート基を有する化合物を含む、<18>または<19>に記載の有機半導体製造用レジスト組成物。
<21>光酸発生剤(A)が、スルホニウムカチオンおよび/またはヨードニウムカチオンを有する化合物を含む、<18>または<19>に記載の有機半導体製造用レジスト組成物。
<22>光酸発生剤(A)が、ジアゾジスルホン化合物および/またはジスルホン化合物を含む、<18>または<19>に記載の有機半導体製造用レジスト組成物。
<23>上記有機半導体製造用レジスト組成物が、光酸発生剤(A)から生じる酸によって極性が変化し、有機溶剤を含む現像液に対する溶解速度が減少する、<18>~<22>のいずれかに記載の有機半導体製造用レジスト組成物。
<24>感光性樹脂組成物が、光酸発生剤(A)から生じる酸によって樹脂(B)に架橋反応が起こることで、有機溶剤を含む現像液に対する溶解速度が減少する、<18>~<23>のいずれかに記載の有機半導体製造用レジスト組成物。
<25>さらに、光酸発生剤(A)を分光増感する増感色素を含む、<18>~<24>のいずれかに記載の有機半導体製造用レジスト組成物。
また、本明細書中における「活性光線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等を意味する。また、本発明において光とは、活性光線または放射線を意味する。本明細書中における「露光」とは、特に断らない限り、水銀灯、エキシマレーザーに代表される遠紫外線、X線、EUV光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も露光に含める。
本発明の積層体は、有機半導体膜と、上記有機半導体膜上の保護膜と、上記保護膜上のレジスト膜を有し、上記レジスト膜が、発生酸のpKaが-1以下の有機酸を発生する光酸発生剤(A)と、上記光酸発生剤から生じる酸に反応して有機溶剤を含む現像液に対する溶解速度が減少する樹脂(B)を含む感光性樹脂組成物からなることを特徴とする。また、有機半導体膜と保護膜との間、および/または保護膜とレジスト膜との間には、下塗り層を有していてもよい。
本発明における感光性樹脂組成物は光酸発生剤を含有し、露光部が有機溶剤を含む現像液に難溶となることでマスクパターンを形成でき、マスクパターンを形成後ドライエッチングのマスクとして利用することが可能になる。
これに対し、本発明では、有機半導体上に保護膜を成膜しその上にレジスト膜を製膜している。この場合、レジスト膜と有機半導体膜が直接に接触しないため、有機半導体膜にダメージが及ぶことを抑制できる。さらに、レジスト膜は感光性樹脂組成物を用いるため、高い保存安定性と微細なパターン形成性を達成できる。
以下、本発明を詳細に説明する。
本発明で用いる有機半導体膜は、半導体の特性を示す有機材料を含む膜のことである。無機材料からなる半導体の場合と同様に、正孔をキャリアとして伝導するp型有機半導体と、電子をキャリアとして伝導するn型有機半導体がある。有機半導体中のキャリアの流れやすさはキャリア移動度μで表される。用途にもよるが、一般に移動度は高い方がよく、10-7cm2/Vs以上であることが好ましく、10-6cm2/Vs以上であることがより好ましく、10-5cm2/Vs以上であることがさらに好ましい。移動度は電界効果トランジスタ(FET)素子を作製したときの特性や飛行時間計測(TOF)法により求めることができる。
溶剤としては、ヘキサン、オクタン、デカン、トルエン、キシレン、エチルベンゼン、1-メチルナフタレン、1,2-ジクロロベンゼン等の炭化水素系溶剤;例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤;例えば、ジクロロメタン、クロロホルム、テトラクロロメタン、ジクロロエタン、トリクロロエタン、テトラクロロエタン、クロロベンゼン、ジクロロベンゼン、クロロトルエン等のハロゲン化炭化水素系溶剤;例えば、酢酸エチル、酢酸ブチル、酢酸アミル等のエステル系溶剤;例えば、メタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、メチルセロソルブ、エチルセロソルブ、エチレングリコール等のアルコール系溶剤;例えば、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソール等のエーテル系溶剤;例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、1-メチル-2-ピロリドン、1-メチル-2-イミダゾリジノン、ジメチルスルホキサイド等の極性溶剤などが挙げられる。これらの溶剤は1種のみを用いてもよいし、2種類以上を用いてもよい。
樹脂バインダーを配合する場合、その配合量は、有機半導体膜中、好ましくは0.1~30質量%で用いられる。
本発明の保護膜は、有機半導体膜の上に形成され、好ましくは、有機半導体膜の表面に形成される。有機半導体膜と保護膜の間には、下塗り層等があっても良い。
保護膜は、有機半導体上に成膜する時に有機半導体にダメージを与えず、また、保護膜上にレジスト膜を塗布した時にインターミキシング(層間混合)を起こさないものが好ましい。保護膜は、水溶性樹脂を含む膜が好ましく、脂溶性樹脂を主成分とする膜であることがより好ましい。主成分とは、保護膜を構成する成分のうち最も多い成分をいい、好ましくは80質量%以上が水溶性樹脂であることをいう。
本発明における水溶性樹脂は、20°Cにおける水に対する溶解度が1%以上である樹脂をいう。
また、保護膜形成用組成物は、2種類以上の樹脂を含んでいてもよいが、この場合、2種類以上の樹脂それぞれが上記範囲を満たしていることが好ましい。
また、これらの中から、主鎖構造が相違する2種以上を選択して使用してもよく、共重合体として使用してもよい。
保護膜用樹脂の分散度(分子量分布)は、通常1.0~3.0であり、好ましくは1.0~2.6の範囲のものが好ましく使用される。
適用方法としては、塗布が好ましい。適用方法の例としては、キャスト法、ブレードコーティング法、ワイヤーバーコーティング法、スプレーコーティング法、ディッピング(浸漬)コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法、インクジェット法、スピンコート法、ラングミュア-ブロジェット(Langmuir-Blodgett)(LB)法などを挙げることができる。本発明においては、キャスト法、スピンコート法、およびインクジェット法を用いることがさらに好ましい。このようなプロセスにより、表面が平滑で大面積の有機半導体膜等の膜を低コストで生産することが可能となる。
上記界面活性剤の例として、日信化学工業(株)製、サーフィノールシリーズが例示される。
保護膜形成用組成物が界面活性剤を含む場合、界面活性剤の添加量は、保護膜としたときに、好ましくは0.05~8質量%、さらに好ましくは0.07~5質量%、特に好ましくは0.1~3質量%の割合で含まれていることが好ましい。
これら界面活性剤は、1種のみ用いてもよいし、2種類以上用いてもよい。
染料は、配合する場合、保護膜の0.1~10質量%とすることができる。
染料は、1種で使用してもよいし、複数併用してもよい。
本発明で用いる感光性樹脂組成物は、有機半導体製造用レジスト組成物としての役割を果たすものであり、保護膜の上にレジスト膜を形成するのに用いられる。
本発明で用いる感光性樹脂組成物は、発生酸のpKaが-1以下の有機酸を発生する光酸発生剤(A)と、上記光酸発生剤から生じる酸に反応して有機溶剤を含む現像液に対する溶解速度が減少する樹脂(B)を含むことを特徴とする。
本発明で用いる感光性樹脂組成物の好ましい第一の実施形態は、光酸発生剤から生ずる有機酸によって極性が変化し、有機溶剤を含む現像液に対する溶解速度が減少する組成物であり、sp値が19(MPa)1/2未満の有機溶剤に対して溶解速度が低下する組成物であることがより好ましく、18.5(MPa)1/2以下の有機溶剤に対して難溶となる組成物であることがさらに好ましく、18.0(MPa)1/2以下の有機溶剤に対して溶解速度が低下する組成物であることがよりさらに好ましい。
また、本発明で用いる感光性樹脂組成物の好ましい第二の実施形態は、光酸発生剤(A)から生じる発生酸によって樹脂(B)に架橋反応が起こることで、有機溶剤を含む現像液に対する溶解速度が減少する組成物である形態である。
本発明では、上記第一および第二の実施形態の両方を満たす態様がより好ましい。
ここで、本発明において「残渣」とは、感光性樹脂組成物を用いてパターン状のレジスト膜を形成した際において、上記パターン状のレジスト膜端部の周縁に存在する残膜を意味する。
本発明で用いる光酸発生剤は、発生酸のpKaが-1以下の有機酸を発生する光酸発生剤である。pKa-1より大きい酸では、樹脂(B)の反応性が不十分となり、有機溶剤を含む現像液に対する溶解速度を十分に減少することができない。また、光酸発生剤(A)が無機酸を発生する場合は、無機酸が保護膜中に拡散しパターンがアンダーカット形状になったり剥がれの原因となる。さらに保護膜と樹脂(B)との間で反応が生じて残渣の原因ともなりうる。本発明では、pKaの下限は特に定めるものではないが、例えば、-10以上であり、好ましくは、-5以上である。
光酸発生剤(A)から発生するpKaが-1以下の有機酸としては、スルホン酸、トリアルキルスルホニルメチド酸およびジアルキルスルホニルイミド酸から選ばれる少なくとも1種であることが好ましい。
本発明で用いる光酸発生剤(A)は、
(i)オキシムスルホネート基を有する化合物(以下、オキシムスルホネート化合物ともいう)およびイミドスルホネート基を有する化合物(以下、イミドスルホネート基ともいう)、
(ii)スルホニウムカチオンを有する化合物(以下、スルホニウム塩ともいう)およびヨードニウムカチオンを有する化合物(以下、ヨードニウム塩ともいう)
(iii)ジアゾジスルホン化合物およびジスルホン化合物(より好ましくは、ジアゾジスルホン化合物)
からなる群の何れかに該当するものが好ましい。
オキシムスルホネート化合物は、オキシムスルホネート基を有していれば特に制限はないが、下記式(2)、後述する式(OS-103)、式(OS-104)、または、式(OS-105)で表されるオキシムスルホネート化合物であることが好ましい。
上記Xにおけるアルキル基およびアルコキシ基は、置換基を有していてもよい。上記Xにおけるアルキル基としては、炭素数1~4の、直鎖状または分岐状アルキル基が好ましい。上記Xにおけるアルコキシ基としては、炭素数1~4の直鎖状または分岐状アルコキシ基が好ましい。上記Xにおけるハロゲン原子としては、塩素原子またはフッ素原子が好ましい。
式(2)におけるmは、0~3の整数を表し、0または1が好ましい。mが2または3であるとき、複数のXは同一でも異なっていてもよい。
上記R4における炭素数1~10のアルキル基の具体例としては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、s-ブチル基、tert-ブチル基、n-アミル基、i-アミル基、s-アミル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基等が挙げられる。
上記R4における炭素数1~10のアルコキシ基の具体例としては、メトキシ基、エトキシ基、n-プロポキシ基、i-プロポキシ基、n-ブトキシ基、n-アミルオキシ基、n-オクチルオキシ基、n-デシルオキシ基等が挙げられる。
上記R4における炭素数1~5のハロゲン化アルキル基の具体例としては、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロ-n-プロピル基、パーフルオロ-n-ブチル基、パーフルオロ-n-アミル基等が挙げられる。
上記R4における炭素数1~5のハロゲン化アルコキシ基の具体例としては、トリフルオロメトキシ基、ペンタフルオロエトキシ基、パーフルオロ-n-プロポキシ基、パーフルオロ-n-ブトキシ基、パーフルオロ-n-アミルオキシ基等が挙げられる。
式(2)で表されるオキシムスルホネート化合物の具体例としては、下記化合物(i)、化合物(ii)、化合物(iii)、化合物(iv)等が挙げられ、これらの化合物は、1種単独で使用してもよいし、2種類以上を併用することもできる。化合物(i)~(iv)は、市販品として、入手することができる。また、その他の式(2)で表されるオキシムスルホネート化合物の具体例を以下に挙げる。
上記式(OS-103)~(OS-105)中、R11で表されるアルキル基としては、置換基を有していてもよい総炭素数1~30のアルキル基であることが好ましい。
R11で表されるアルキル基が有していてもよい置換基としては、ハロゲン原子、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基が挙げられる。
R11で表されるアリール基が有していてもよい置換基としては、ハロゲン原子、アルキル基、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基、スルホン酸基、アミノスルホニル基、アルコキシスルホニル基が挙げられる。
R11で表されるヘテロアリール基が有していてもよい置換基としては、ハロゲン原子、アルキル基、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基、スルホン酸基、アミノスルホニル基、アルコキシスルホニル基が挙げられる。
R11で表されるヘテロアリール基としては、置換基を有していてもよい、チオフェン環、ピロール環、チアゾール環、イミダゾール環、フラン環、ベンゾチオフェン環、ベンゾチアゾール環、および、ベンゾイミダゾール環よりなる群から選ばれた環から1つの水素原子を除いた基が挙げられる。
上記式(OS-103)~(OS-105)中、化合物中に2以上存在するR12のうち、1つまたは2つがアルキル基、アリール基またはハロゲン原子であることが好ましく、1つがアルキル基、アリール基またはハロゲン原子であることがより好ましく、1つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。
上記式(OS-103)~(OS-105)中、R12で表されるアルキル基またはアリール基は、置換基を有していてもよい。
R12で表されるアルキル基またはアリール基が有していてもよい置換基としては、上記R1におけるアルキル基またはアリール基が有していてもよい置換基と同様の基が例示できる。
R12で表されるアルキル基としては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、s-ブチル基、n-ヘキシル基、アリル基、クロロメチル基、ブロモメチル基、メトキシメチル基、ベンジル基が好ましく、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、s-ブチル基、n-ヘキシル基がより好ましく、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ヘキシル基がさらに好ましく、メチル基が特に好ましい。
R12で表されるアリール基としてフェニル基、p-メチルフェニル基、o-クロロフェニル基、p-クロロフェニル基、o-メトキシフェニル基、p-フェノキシフェニル基が好ましい。
R12で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。これらの中でも、塩素原子、臭素原子が好ましい。
上記式(OS-103)~(OS-105)中、nは1または2を表し、XがOである場合、nは1であることが好ましく、また、XがSである場合、nは2であることが好ましい。
上記式(OS-103)~(OS-105)中、R16で表されるアルキル基としては、置換基を有していてもよい総炭素数1~30のアルキル基であることが好ましい。
R16で表されるアルキル基が有していてもよい置換基としては、ハロゲン原子、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基が挙げられる。
R16で表されるアルキルオキシ基が有していてもよい置換基としては、ハロゲン原子、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基が挙げられる。
R16におけるアミノスルホニル基としては、メチルアミノスルホニル基、ジメチルアミノスルホニル基、フェニルアミノスルホニル基、メチルフェニルアミノスルホニル基、アミノスルホニル基が挙げられる。
R16で表されるアルコキシスルホニル基としては、メトキシスルホニル基、エトキシスルホニル基、プロピルオキシスルホニル基、ブチルオキシスルホニル基が挙げられる。
上記式(OS-106)におけるR17は、水素原子または臭素原子を表し、水素原子であることが好ましい。
上記式(OS-106)~(OS-111)におけるR18は、水素原子、炭素数1~8のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基またはクロロフェニル基を表し、炭素数1~8のアルキル基、ハロゲン原子またはフェニル基であることが好ましく、炭素数1~8のアルキル基であることがより好ましく、炭素数1~6のアルキル基であることがさらに好ましく、メチル基であることが特に好ましい。
上記式(OS-108)および(OS-109)におけるR19は、水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、水素原子であることが好ましい。
上記式(OS-108)~(OS-111)におけるR20は、水素原子またはメチル基を表し、水素原子であることが好ましい。
また、上記オキシムスルホネート化合物において、オキシムの立体構造(E,Z)については、どちらか一方であっても、混合物であってもよい。
Xは-O-、-S-、-NH-、-NR15-、-CH2-、-CR16H-または-CR16R17-を表し、R15~R17はそれぞれ独立に、アルキル基またはアリール基を表す。
R21~R24はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基またはアリール基を表す。R21~R24のうち2つは、それぞれ互いに結合して環を形成してもよい。
R21~R24としては、水素原子、ハロゲン原子またはアルキル基が好ましく、また、R21~R24のうち少なくとも2つが互いに結合してアリール基を形成する態様もまた、好ましく挙げられる。中でも、R21~R24がいずれも水素原子である態様が、感度の観点から好ましい。
上記した置換基は、いずれも、さらに置換基を有していてもよい。
これらの中でも、式(OS-101)および式(OS-102)におけるR11がシアノ基またはアリール基である態様がより好ましく、式(OS-102)で表され、R11がシアノ基、フェニル基またはナフチル基である態様が最も好ましい。
市販品としては、WPAG-336(和光純薬工業(株)製)、WPAG-443(下記構造、和光純薬工業(株)製)、MBZ-101(下記構造、みどり化学(株)製)等をあげることができる。
R208のアルキル基は、直鎖アルキル基または環状アルキル基が好ましい。R208は、直鎖または分岐のアルキル基、またはアリール基が好ましい。これらの基は、置換されていてもよく、置換されていなくてもよい。また、アルキル基が環状アルキル基の場合、カルボニル基を介して環を形成していてもよく、環状アルキル基は、多環式であってもよい。好ましくは、炭素数1~10の直鎖又は分岐鎖アルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基又はペンチル基)及び炭素数3~10のシクロアルキル基(シクロペンチル基、シクロヘキシル基又はノルボニル基)が挙げられる。R208のアルキル基は、例えば、ハロゲン原子、アルコキシ基(例えば炭素数1~5)、水酸基、シアノ基及び/又はニトロ基によって更に置換されていてもよい。
R208ノアリール基は、例えば、ハロゲン原子、アルコキシ基(例えば炭素数1~5)、水酸基、シアノ基及び/又はニトロ基によって更に置換されていてもよいが、好ましくは、炭素数1~10の直鎖又は分岐鎖アルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基又はペンチル基)及び炭素数3~10のシクロアルキル基(シクロペンチル基、シクロヘキシル基又はノルボニル基)が挙げられる。
以下に、イミドスルホネート化合物の例を挙げるが本発明はこれらに限定されるものではない。
(ii)スルホニウム塩、ヨードニウム塩スルホニウム塩またはヨードニウム塩は、アニオンが非求核性であり、光分解してpKaが-1以下の有機酸を発生する化合物であれば特に制限はないが、アニオンとしてスルホン酸アニオン、スルホニルイミドアニオン、ビス(アルキルスルホニル)イミドアニオン、トリス(アルキルスルホニル)メチルアニオンを有しているものが好適である。
より好ましくは下記一般式(ZI)、(ZII)、(ZIII)で表される化合物を挙げることができる。
R201、R202およびR203は、各々独立に、有機基を表す。
R201、R202およびR203としての有機基の炭素数は、一般的に1~30、好ましくは1~20である。
また、R201~R203のうち2つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル結合、アミド結合、カルボニル基を含んでいてもよい。R201~R203の内の2つが結合して形成する基としては、アルキレン基(例えば、ブチレン基、ペンチレン基)を挙げることができる。
Z-は、スルホン酸アニオン(脂肪族スルホン酸アニオン、芳香族スルホン酸アニオン、カンファースルホン酸アニオンなど)、カルボン酸アニオン(脂肪族カルボン酸アニオン、芳香族カルボン酸アニオン、アラルキルカルボン酸アニオンなど)、スルホニルイミドアニオン、ビス(アルキルスルホニル)イミドアニオン、トリス(アルキルスルホニル)メチドアニオン等を挙げられる。
また、ビス(アルキルスルホニル)イミドアニオンにおけるアルキル基は、互いに結合して環構造を形成してもよい。これにより、酸強度が増加する。
Z-としては、保護膜層の上に感光性樹脂組成物を塗布する際のインターミキシング(保護膜中へのスルホニウム塩、ヨードニウム塩の層間混入)を抑制する観点から、カチオン中に、炭素数3以上のアルキル基を置換基として有する芳香環基を含むことが好ましい。上記アルキル基としては炭素数6以上が好ましく、さらに好ましくは8以上である。アルキル基としては、直鎖、分岐、環状いずれであってもよく、具体的には、n-プロピル、i-プロピル、n-ブチル、i-ブチル、tert-ブチル、n-アミル、i-アミル、tert-アミル、n-ヘキシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、n-オクチル、2-エチルヘキシルといった基が挙げられる。
同様にアニオンについても、炭素数6以上のアルキル基を含むスルホネート、もしくは炭素数3以上のアルキル基を置換基として有する芳香環を含むスルホネートであることが好ましい。
Xfは、それぞれ独立に、フッ素原子、または少なくとも1つのフッ素原子で置換されたアルキル基を表す。
R1、R2は、それぞれ独立に、水素原子、フッ素原子、または、アルキル基を表し、複数存在する場合のR1、R2は、それぞれ同一でも異なっていてもよい。
Lは、二価の連結基を表し、複数存在する場合のLは同一でも異なっていてもよい。
Aは、環状の有機基を表す。
xは0~20の整数を表し、yは0~10の整数を表し、zは0~10の整数を表す。
Xfのフッ素原子で置換されたアルキル基におけるアルキル基としては、好ましくは炭素数1~10であり、より好ましくは炭素数1~4である。また、Xfのフッ素原子で置換されたアルキル基は、パーフルオロアルキル基であることが好ましい。Xfとして好ましくは、フッ素原子または炭素数1~4のパーフルオロアルキル基である。Xfの具体的としては、フッ素原子、CF3、C2F5、C3F7、C4F9、CH2CF3、CH2CH2CF3、CH2C2F5、CH2CH2C2F5、CH2C3F7、CH2CH2C3F7、CH2C4F9、CH2CH2C4F9が挙げられ、中でもフッ素原子、CF3が好ましい。特に、双方のXfがフッ素原子であることが好ましい。
R1、R2としては、好ましくはフッ素原子またはCF3である。
yは0~8が好ましく、0~6がより好ましい。
zは0~5が好ましく、0~3がより好ましい。
Lの2価の連結基としては特に限定されず、―COO-、-OCO-、-CO-、-O-、-S―、-SO―、―SO2-、アルキレン基、シクロアルキレン基、アルケニレン基またはこれらの複数が連結した連結基などを挙げることができ、総炭素数12以下の連結基が好ましい。このなかでも―COO-、-OCO-、-CO-、-O-が好ましく、―COO-、-OCO-がより好ましい。
脂環基としては、単環でも多環でもよく、シクロペンチル基、シクロヘキシル基、シクロオクチル基などの単環のシクロアルキル基、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。中でも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基等の炭素数7以上のかさ高い構造を有する脂環基が、露光後加熱工程での膜中拡散性を抑制でき、MEEF向上の観点から好ましい。
アリール基としては、ベンゼン環、ナフタレン環、フェナンスレン環、アントラセン環が挙げられる。
複素環基としては、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、ピリジン環由来のものが挙げられる。中でもフラン環、チオフェン環、ピリジン環由来のものが好ましい。
R201、R202およびR203のうち、少なくとも1つがアリール基であることが好ましく、三つ全てがアリール基であることがより好ましい。アリール基としては、フェニル基、ナフチル基などの他に、インドール残基、ピロール残基などのヘテロアリール基も可能である。R201~R203のアルキル基およびシクロアルキル基としては、好ましくは、炭素数1~10の直鎖または分岐アルキル基、炭素数3~10のシクロアルキル基を挙げることができる。アルキル基として、より好ましくはメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基等を挙げることができる。シクロアルキル基として、より好ましくは、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロへプチル基等を挙げることができる。これらの基はさらに置換基を有していてもよい。その置換基としては、ニトロ基、フッ素原子などのハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基(好ましくは炭素数1~15)、シクロアルキル基(好ましくは炭素数3~15)、アリール基(好ましくは炭素数6~14)、アルコキシカルボニル基(好ましくは炭素数2~7)、アシル基(好ましくは炭素数2~12)、アルコキシカルボニルオキシ基(好ましくは炭素数2~7)等が挙げられるが、これらに限定されるものではない。
R1a~R13aは、各々独立に、水素原子または置換基を表す。
R1a~R13aのうち、1~3つが水素原子でないことが好ましく、R9a~R13aのいずれか1つが水素原子でないことがより好ましい。
Zaは、単結合または2価の連結基である。
X-は、一般式(ZI)におけるZ-と同義である。
R1a~R13aが水素原子でない場合としては、水酸基で置換された直鎖、分岐、環状のアルキル基であることが好ましい。
R204~R205のアリール基としては、前述の化合物(ZI)におけるR201~R203のアリール基として説明したアリール基と同様である。
R204~R205のアリール基は、置換基を有していてもよい。この置換基としても、前述の化合物(ZI)におけるR201~R203のアリール基が有していてもよいものが挙げられる。
R206~R207は、各々独立に、アリール基またはアルキル基を表す。
R206~R207のアリール基、アルキル基としては、前述の化合物(ZI)におけるR201~R203のアリール基、アルキル基として説明したアリール基、アルキル基と同様である。
R206~R207のアリール基、アルキル基、は、置換基を有していてもよい。この置換基としても、前述の化合物(ZI)におけるR201~R203のアリール基、アルキル基が有していてもよいものが挙げられる。
ジスルホン化合物としては、下記一般式(ZIV)で示される化合物が挙げられる。
Ar3、Ar4のアリール基の具体例としては、上記一般式(ZI)におけるR201、R202およびR203としてのアリール基の具体例と同様のものを挙げることができる。
これに対して、本発明では、活性光線に感応して生成する酸を発生する光酸発生剤と、酸の作用により分解が促進される樹脂もしくは、酸の作用により架橋が促進される樹脂を用いることで高感度が得られる。
本発明における感光性樹脂組成物において、酸発生剤は、感光性樹脂組成物の全固形分に対して、0.1~20重量%使用することが好ましく、0.5~18重量%使用することがより好ましい。
本発明で用いる樹脂(B)は、極性基が酸の作用により分解して脱離する脱離基で保護された基(以下、「酸分解性基」ともいう)を有する繰り返し単位を含む樹脂(B-1)、および/または、酸の作用により樹脂(B)の分子鎖間に架橋が生じる(以下、「架橋性基」ともいう)を有する繰り返し単位を含む樹脂(B-2)であることが好ましい。また、架橋剤によって樹脂間で架橋構造を形成する樹脂(B-3)を用いることも好ましい。
樹脂(B-1)を用いることにより、光酸発生剤から生ずる有機酸によって極性が変化し、有機溶剤を含む現像液に対する溶解速度が減少する組成物を得ることができ、樹脂(B-2)を用いることにより、光酸発生剤(A)から生じる発生酸によって樹脂(B)に架橋反応が起こることで、有機溶剤を含む現像液に対する溶解速度が減少する組成物を得ることができる。
本発明では、樹脂(B-1)と樹脂(B-2)を組み合わせる樹脂も好ましい。
<酸分解性基>
酸分解性基が酸の作用により分解して生成する極性基としては、有機溶剤を含む現像液中で難溶化または不溶化する基であれば特に限定されないが、カルボキシル基、スルホン酸基等の酸性基(従来レジストの現像液として用いられている、2.38質量%テトラメチルアンモニウムヒドロキシド水溶液中で解離する基)、水酸基(アルコール性水酸基、フェノール性水酸基など)等が挙げられる。
なお、アルコール性水酸基とは、炭化水素基に結合した水酸基であって、芳香環上に直接結合した水酸基(フェノール性水酸基)以外の水酸基をいい、酸基としてα位がフッ素原子などの電子求引性基で置換された脂肪族アルコール(例えば、フッ素化アルコール基(ヘキサフルオロイソプロパノール基など))は除くものとする。アルコール性水酸基としては、pKaが12以上且つ20以下の水酸基であることが好ましい。
酸で脱離する基としては、例えば、-C(R36)(R37)(R38)、-C(R36)(R37)(OR39)、-C(R01)(R02)(OR39)等を挙げることができる。
上記一般式中、R36~R39は、各々独立に、アルキル基、アリール基、アラルキル基またはアルケニル基を表す。R36とR37とは、互いに結合して環を形成してもよい。アルキル基は、直鎖、分岐または環状のアルキル基である。
R01およびR02は、各々独立に、水素原子、アルキル基、アリール基、アラルキル基またはアルケニル基を表す。
R36~R39、R01およびR02の直鎖または分岐のアルキル基は、炭素数1~8のアルキル基が好ましく、例えば、メチル基、エチル基、プロピル基、n-ブチル基、sec-ブチル基、へキシル基、オクチル基等を挙げることができる。
R36~R39、R01およびR02のシクロアルキル基は、単環型でも、多環型でもよい。単環型としては、炭素数3~8のシクロアルキル基が好ましく、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロオクチル基等を挙げることができる。多環型としては、炭素数6~20のシクロアルキル基が好ましく、例えば、アダマンチル基、ノルボルニル基、イソボロニル基、カンファニル基、ジシクロペンチル基、α-ピネル基、トリシクロデカニル基、テトラシクロドデシル基、アンドロスタニル基等を挙げることができる。なお、シクロアルキル基中の少なくとも1つの炭素原子が酸素原子等のヘテロ原子によって置換されていてもよい。
R36~R39、R01およびR02のアリール基は、炭素数6~10のアリール基が好ましく、例えば、フェニル基、ナフチル基、アントリル基等を挙げることができる。
R36~R39、R01およびR02のアラルキル基は、炭素数7~12のアラルキル基が好ましく、例えば、ベンジル基、フェネチル基、ナフチルメチル基等を挙げることができる。
R36~R39、R01およびR02のアルケニル基は、炭素数2~8のアルケニル基が好ましく、例えば、ビニル基、アリル基、ブテニル基、シクロへキセニル基等を挙げることができる。
R36とR37とが結合して形成される環としては、シクロアルキル基(単環若しくは多環)であることが好ましい。シクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。炭素数5~6の単環のシクロアルキル基がより好ましく、炭素数5の単環のシクロアルキル基が特に好ましい。
樹脂(B-1)が含む酸分解性基を有する繰り返し単位としては、下記一般式(III)で表される繰り返し単位であることが好ましい。
R0は、水素原子または直鎖若しくは分岐のアルキル基を表す。
R1~R3は、それぞれ独立に、直鎖若しくは分岐のアルキル基、または単環若しくは多環のシクロアルキル基を表す。
R1~R3の2つが結合して、単環若しくは多環のシクロアルキル基を形成してもよい。
R0としては水素原子、メチル基、トリフルオロメチル基またはヒドロキシメチル基であることが好ましい。
R1~R3のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基などの炭素数1~4のものが好ましい。
R1~R3のシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。
R1~R3の2つが結合して形成されるシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。炭素数5または6の単環のシクロアルキル基が特に好ましい。
好ましい態様の1つとしては、R1がメチル基またはエチル基であり、R2とR3とが結合して上述のシクロアルキル基を形成している態様が挙げられる。
上記各基は、置換基を有していてもよく、置換基としては、例えば、水酸基、ハロゲン原子(例えば、フッ素原子)、アルキル基(炭素数1~4)、シクロアルキル基(炭素数3~8)、アルコキシ基(炭素数1~4)、カルボキシル基、アルコキシカルボニル基(炭素数2~6)などが挙げられ、炭素数8以下が好ましい。
上記一般式(III)で表される繰り返し単位の特に好ましい態様としては、R1、R2およびR3は、各々独立に、直鎖または分岐のアルキル基を表す態様である。
この態様において、R1、R2およびR3についての直鎖または分岐のアルキル基としては、炭素数1~4のアルキル基であることが好ましく、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基が挙げられる。
R1としては、メチル基、エチル基、n-プロピル基、n-ブチル基が好ましく、メチル基、エチル基がより好ましく、メチル基が特に好ましい。
R2としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基が好ましく、メチル基、エチル基がより好ましく、メチル基が特に好ましい。
R3としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基が好ましく、メチル基、エチル基、イソプロピル基、イソブチル基がより好ましく、メチル基、エチル基、イソプロピル基が特に好ましい。
具体例中、Rxは、水素原子、CH3、CF3、またはCH2OHを表す。Rxa、Rxbはそれぞれ炭素数1~4のアルキル基を表す。Zは、置換基を表し、複数存在する場合、複数のZは互いに同じであっても異なっていてもよい。pは0または正の整数を表す。Zの具体例および好ましい例は、R1~R3などの各基が有し得る置換基の具体例および好ましい例と同様である。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示され、これらの中でもフッ素原子または塩素原子が好ましい。
また、上記アリール基としては、炭素数6~20のアリール基が好ましく、より好ましくは炭素数6~12であり、具体的には、フェニル基、α-メチルフェニル基、ナフチル基等が例示でき、アリール基で置換されたアルキル基全体、すなわち、アラルキル基としては、ベンジル基、α-メチルベンジル基、フェネチル基、ナフチルメチル基等が例示できる。
上記アルコキシ基としては、炭素数1~6のアルコキシ基が好ましく、より好ましくは炭素数1~4であり、メトキシ基またはエトキシ基がより好ましい。
また、アルキル基がシクロアルキル基である場合、上記シクロアルキル基は置換基として炭素数1~10の直鎖状または分岐鎖状のアルキル基を有していてもよく、アルキル基が直鎖状または分岐鎖状のアルキル基である場合には、置換基として炭素数3~12のシクロアルキル基を有していてもよい。
これらの置換基は、上記置換基でさらに置換されていてもよい。
一般式(XP)
R1及びR2がアルキル基の場合、炭素数は1~10のアルキル基が好ましい。R1及びR2がアリール基の場合、フェニル基が好ましい。R1及びR2は、それぞれ、水素原子又は炭素数1~4のアルキル基が好ましい。
R3は、アルキル基又はアリール基を表し、炭素数1~10のアルキル基が好ましく、1~6のアルキル基がより好ましい。
Xはフェニレン基が好ましい。
以下に、一般式(XP)で表される繰り返し単位の例を示すが、本発明はこれらに限定されるものではないことは言うまでもない。
他の繰り返し単位としては、一般式(I)で表される繰り返し単位、上記一般式(I)で表される繰り返し単位以外の非フェノール系芳香族基を有する繰り返し単位、ラクトン構造を有する繰り返し単位、酸基を有する繰り返し単位、水酸基および/またはシアノ基を有する繰り返し単位、極性基を持たない脂環炭化水素構造を有し、酸分解性を示さない繰り返し単位が例示される。
本発明において、樹脂(A)中の全繰り返し単位に対して、下記一般式(I)で表される繰り返し単位を含有していてもよい。
Xaは水素原子または直鎖若しくは分岐のアルキル基を表す。
Rxは水素原子または酸の作用により分解し脱離する基を表す。
Rxについての酸の作用により分解し脱離する基の具体例および好ましい例としては、樹脂(B-1)における酸分解性基を構成する極性基を保護している酸の作用により分解し脱離する基の具体例および好ましい例として前述したものと同様のものが挙げられる。
本発明において、樹脂(B-1)は、上記一般式(I)で表される繰り返し単位以外の非フェノール系芳香族基を有する繰り返し単位を有することが好ましい。
ここで、「上記一般式(I)で表される繰り返し単位以外の非フェノール系芳香族基を有する繰り返し単位」とは、上記一般式(I)で表される繰り返し単位などの、フェノール性水酸基を有する芳香族基を有する繰り返し単位、フェノール性水酸基から誘導される基(例えば、フェノール性水酸基が酸の作用により分解し脱離する基で保護された基など)を有する芳香族基を有する繰り返し単位以外のフェノール性水酸基を有しない芳香族基を有する繰り返し単位をいう。
上記非フェノール系芳香族基としては、置換基を有していてもよく、炭素数6~10のアリール基であることが好ましく、例えば、フェニル基、ナフチル基が挙げられる。
上記置換基としては、フェノール性水酸基ではない限り特に制限はなく、炭素数1~4の直鎖状若しくは分枝状のアルキル基、炭素数3~10のシクロアルキル基、炭素数6~10のアリール基、フッ素原子などのハロゲン原子、シアノ基、アミノ基、ニトロ基、カルボキシル基などが挙げられる。上記置換基としての炭素数1~4の直鎖状若しくは分枝状のアルキル基、炭素数3~10のシクロアルキル基、炭素数6~10のアリール基はさらに置換基を有していてもよく、そのような更なる置換基としては、フッ素原子などのハロゲン原子などが挙げられる。
上記非フェノール系芳香族基がフェニル基であり、上記フェニル基が置換基を有する場合、上記置換基はフェニル基の4位に置換することが好ましい。
上記非フェノール系芳香族基としては、エッチング耐性の点から、置換基を有していてもよいフェニル基が好ましい。
R01は、水素原子または直鎖若しくは分岐のアルキル基を表す。
Xは単結合または2価の連結基を表す。
Arは非フェノール系芳香族基を表す。
R4は、単結合またはアルキレン基を表す。
Xは、2価の連結基が好ましい。この2価の連結基としては、好ましくは-COO-、-CONH-などが挙げられる。
非フェノール系芳香族基Arの具体例および好ましい例としては、非フェノール系芳香族基の具体例および好ましい例として前述したものと同様のものが挙げられる。
R4についてのアルキレン基としては、置換基を有していてもよく、炭素数1~4のアルキレン基であることが好ましく、メチレン基、エチレン基、プロピレン基などが挙げられる。R4についてのアルキレン基が有し得る置換基としては、炭素数1~4のアルキル基、フッ素原子などのハロゲン原子などが挙げられる。
R4についてのアルキレン基が有し得る置換基と非フェノール系芳香族基Arが有し得る置換基とが結合して環を形成していてもよく、上記環を形成する基としては、アルキレン基(例えば、エチレン基、プロピレン基)を挙げることができる。
R4としては、パターン形成における樹脂の好適なガラス転移温度(Tg)の観点から、単結合、または置換基で置換されていてよいメチレン基であることが好ましい。
樹脂(B-1)は、さらに、ラクトン構造を有する繰り返し単位を有していてもよい。ラクトン構造を有する繰り返し単位としては、下記一般式(AII)で表される繰り返し単位がより好ましい。
Rb0は、水素原子、ハロゲン原子または置換基を有していてもよいアルキル基(好ましくは炭素数1~4)を表す。
Rb0のアルキル基が有していてもよい好ましい置換基としては、水酸基、ハロゲン原子が挙げられる。Rb0のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子を挙げることができる。Rb0として、好ましくは、水素原子、メチル基、ヒドロキシメチル基、トリフルオロメチル基であり、水素原子、メチル基が特に好ましい。
Ab1は、直鎖または分岐アルキレン基、単環または多環のシクロアルキレン基であり、好ましくはメチレン基、エチレン基、シクロヘキシレン基、アダマンチレン基、ノルボルニレン基である。
Vは、ラクトン構造を有する基を表す。
以下に、樹脂(B-1)中のラクトン構造を有する繰り返し単位の具体例を示すが、本発明はこれに限定されるものではない。式中、Rxは、H、CH3、CH2OHまたはCF3を表す。
樹脂(B-1)は、酸基を有する繰り返し単位を有してもよい。酸基としてはカルボキシル基、スルホンアミド基、スルホニルイミド基、ビススルホニルイミド基、α位が電子求引性基で置換された脂肪族アルコール(例えばヘキサフロロイソプロパノール基)が挙げられ、カルボキシル基を有する繰り返し単位を有することがより好ましい。酸基を有する繰り返し単位を含むことによりコンタクトホール用途などでの解像性が増す。酸基を有する繰り返し単位としては、アクリル酸、メタクリル酸による繰り返し単位のような樹脂の主鎖に直接酸基が結合している繰り返し単位、あるいは連結基を介して樹脂の主鎖に酸基が結合している繰り返し単位、さらには酸基を有する重合開始剤や連鎖移動剤を重合時に用いてポリマー鎖の末端に導入、のいずれも好ましく、連結基は単環または多環の環状炭化水素構造を有していてもよい。特に好ましくはアクリル酸、メタクリル酸による繰り返し単位である。
酸基を有する繰り返し単位の具体例を以下に示すが、本発明は、これに限定されるものではない。
具体例中、RxはH、CH3、CH2OHまたはCF3を表す。
樹脂(B-1)は、水酸基又はシアノ基を有する繰り返し単位を有していても良い。これにより基板密着性、現像液親和性が向上する。水酸基又はシアノ基を有する繰り返し単位は、水酸基又はシアノ基で置換された炭化水素構造を有する繰り返し単位であることが好ましい。炭化水素構造は、直鎖、分岐または環状構造の脂肪族炭化水素基であることが好ましく、脂環炭化水素構造を有する繰り返し単位であることがより好ましい。また、水酸基および/またはシアノ基を有する繰り返し単位は、酸分解性基を有さないことが好ましい。
また、水酸基又はシアノ基で置換された脂環炭化水素構造を有する繰り返し単位は、酸分解性基を有する繰り返し単位とは異なることが好ましい(すなわち、酸に対して安定な繰り返し単位であることが好ましい)。
水酸基又はシアノ基で置換された脂環炭化水素構造に於ける、脂環炭化水素構造としては、アダマンチル基、ジアマンチル基、ノルボルナン基が好ましい。
より好ましくは、下記一般式(AIIa)~(AIIc)のいずれかで表される繰り返し単位を挙げることができる。
Abは、単結合、又は2価の連結基を表す。
Abにより表される2価の連結基としては、例えば、アルキレン基、シクロアルキレン基、エステル結合、アミド結合、エーテル結合、ウレタン結合、ウレア結合、又はその組み合わせ等が挙げられる。アルキレン基としては、炭素数1~10のアルキレン基が好ましく、炭素数1~5のアルキレン基がより好ましく、例えば、メチレン基、エチレン基、プロピレン基等が挙げられる。
本発明の一形態において、Abは、単結合、又は、アルキレン基であることが好ましい。
Rpは、水素原子、ヒドロキシル基、又は、ヒドロキシアルキル基を表す。複数のRpは、同一でも異なっていても良いが、複数のRpの内の少なくとも1つは、ヒドロキシル基又はヒドロキシアルキル基を表す。
水酸基又はシアノ基を有する繰り返し単位の具体例を以下に挙げるが、本発明はこれらに限定されない。
本発明における樹脂(B-1)は、さらに極性基(例えば、上記酸基、水酸基、シアノ基)を持たない炭化水素構造を有し、酸分解性を示さない繰り返し単位を有することができる。これにより、有機溶剤を含む現像液を用いた現像の際に樹脂の溶解性を適切に調整することができる。このような繰り返し単位としては、一般式(IV)で表される繰り返し単位が挙げられる。
Raは水素原子、アルキル基または-CH2-O-Ra2基を表す。式中、Ra2は、水素原子、アルキル基またはアシル基を表す。Raは、水素原子、メチル基、ヒドロキシメチル基、トリフルオロメチル基が好ましく、水素原子、メチル基が特に好ましい。
R5の極性基を有さない炭化水素基は、環状構造を有していても良い。環状構造としては、単環式炭化水素基および多環式炭化水素基が含まれる。単環式炭化水素基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロへプチル基、シクロオクチル基などの炭素数3~12のシクロアルキル基、シクロへキセニル基など炭素数3~12のシクロアルケニル基が挙げられる。好ましい単環式炭化水素基としては、炭素数3~7の単環式炭化水素基であり、より好ましくは、シクロペンチル基、シクロヘキシル基が挙げられる。
極性基を持たない炭化水素構造を有し、酸分解性を示さない繰り返し単位の具体例を以下に挙げるが、本発明はこれらに限定されない。式中、Raは、H、CH3、CH2OH、またはCF3を表す。
樹脂(B-2)は、酸の作用により樹脂(B)の分子鎖間に架橋が生じる基(以下、「架橋性基」ともいう)を有する繰り返し単位を含む樹脂(B-2a)、後述する架橋剤を介して樹脂(B)の分子鎖間に架橋が形成する樹脂(B-2b)がある。
樹脂(B-2a)の場合、架橋基は、酸存在下、加熱処理で硬化反応を起こす基であれば特に限定はされない。好ましい架橋基を有する繰り返し単位の態様としては、エポキシ基、オキセタニル基、-NH-CH2-OR(Rは炭素数1~20のアルキル基)およびビニルエーテル基よりなる群から選ばれた少なくとも1つを含む繰り返し単位が挙げられる。
その中でも、本発明の感光性樹脂組成物は、上記(A)成分が、エポキシ基およびオキセタニル基のうち少なくとも1つを含む繰り返し単位を含むことがより好ましく、オキセタニル基を含む繰り返し単位を含むことが特に好ましい。より詳細には、以下のものが挙げられる。
上記(A)共重合体は、エポキシ基および/またはオキセタニル基を有する繰り返し単位を含むことが好ましい。上記3員環の環状エーテル基はエポキシ基とも呼ばれ、4員環の環状エーテル基はオキセタニル基とも呼ばれる。上記エポキシ基および/またはオキセタニル基を有する繰り返しとが好ましく、オキセタニル基を有する繰り返し単位であることがより好ましい。
上記エポキシ基および/またはオキセタニル基を有する繰り返しは、1つの繰り返し単位中にエポキシ基またはオキセタニル基を少なくとも1つ有していればよく、1つ以上のエポキシ基および1つ以上オキセタニル基、2つ以上のエポキシ基、または、2つ以上のオキセタニル基を有していてもよく、特に限定されないが、エポキシ基および/またはオキセタニル基を合計1~3つ有することが好ましく、エポキシ基および/またはオキセタニル基を合計1または2つ有することがより好ましく、エポキシ基またはオキセタニル基を1つ有することがさらに好ましい。
オキセタニル基を有する繰り返し単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、特開2001-330953号公報の段落0011~0016に記載のオキセタニル基を有する(メタ)アクリル酸エステルなどを挙げることができる。
上記エポキシ基および/またはオキセタニル基を有する繰り返しを形成するために用いられるラジカル重合性単量体の具体例としては、メタクリル酸エステル構造を含むモノマー、アクリル酸エステル構造を含むモノマーであることが好ましい。
本発明で用いる共重合体は、-NH-CH2-O-R(Rは炭素数1~20のアルキル基)を有する繰り返し単位も好ましい。これにより緩やかな加熱処理で硬化反応を起こすことができ、諸特性に優れた硬化膜を得ることができる。ここで、Rは炭素数1~9のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。繰り返し単位は、より好ましくは、下記一般式(1)で表される基を有する繰り返し単位である。
一般式(1)
R2は、炭素数1~9のアルキル基が好ましく、炭素数1~4のアルキル基がさらに好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。
R2の具体例としては、メチル基、エチル基、n-ブチル基、i-ブチル基、シクロヘキシル基、およびn-ヘキシル基を挙げることができる。中でもi-ブチル基、n-ブチル基、メチル基が好ましい。
本発明で用いる共重合体は、ビニルエーテル基を有する繰り返し単位も好ましい。具体的には下記一般式で表される繰り返し単位が、その例として挙げられる。
Rveはビニルエーテル基を末端に有する基であり、具体的には2-(ビニルオキシ)アルキル基が好ましい。ここでアルキル基としては炭素数2~6のアルキル基が好ましく、その中でも2-(ビニルオキシ)エチル基が好ましい。
次に、樹脂(B-2b)について説明する。
樹脂(B-2b)は、以下に記載する架橋剤と反応して結合を形成する繰り返し単位を含む。この様な繰り返し単位としては、 他の繰り返し単位としては、一般式(I)で表される繰り返し単位、上記一般式(I)で表される繰り返し単位以外の非フェノール系芳香族基を有する繰り返し単位、ラクトン構造を有する繰り返し単位、水酸基および/またはシアノ基を有する繰り返し単位、酸基を有する繰り返し単位、極性基を持たない脂環炭化水素構造を有し、酸分解性を示さない繰り返し単位が例示される。これらは、樹脂(B-1)の記載を参酌でき、好ましい範囲も同義である。
このような樹脂の例としては、上記一般式(I)で表される繰り返し単位であって、Rxが水素原子である繰り返し単位、上記一般式(I)で表される繰り返し単位以外の非フェノール系芳香族基を有する繰り返し単位であって、Arがフェニル基の場合が例示される。さらに、上記で述べたその他の繰り返し単位(架橋性基を有する繰り返し単位、酸分解性基を有する繰り返し単位等、特に酸分解性基を有する繰り返し単位)を有していても良い。
樹脂(B-3)は、ベンゼン環および/またはフェノール性水酸基を有する繰り返し単位が、全繰り返し単位の50~100モル%であることが好ましい。
これにより、本発明における感光性樹脂組成物に用いられる樹脂に要求される性能、特に、
(1)塗布溶剤に対する溶解性、
(2)製膜性(ガラス転移点)、
(3)アルカリ現像性、
(4)膜厚減り(親疎水性、アルカリ可溶性基選択)、
(5)未露光部の基板への密着性、
(6)ドライエッチング耐性等の微調整が可能となる。
その他にも、上記種々の繰り返し単位に相当する単量体と共重合可能である付加重合性の不飽和化合物であれば、共重合されていてもよい。
本発明における樹脂(B)の形態としては、ランダム型、ブロック型、クシ型、スター型のいずれの形態でもよい。樹脂(B)は、例えば、各構造に対応する不飽和モノマーのラジカル、カチオン、またはアニオン重合により合成することができる。また各構造の前駆体に相当する不飽和モノマーを用いて重合した後に、高分子反応を行うことにより目的とする樹脂を得ることも可能である。
沈殿または再沈殿する際の温度としては、効率や操作性を考慮して適宜選択できるが、通常0~50℃程度、好ましくは室温付近(例えば20~35℃程度)である。沈殿または再沈殿操作は、攪拌槽などの慣用の混合容器を用い、バッチ式、連続式等の公知の方法により行うことができる。
沈殿または再沈殿したポリマーは、通常、濾過、遠心分離等の慣用の固液分離に付し、乾燥して使用に供される。濾過は、耐溶剤性の濾材を用い、好ましくは加圧下で行われる。乾燥は、常圧または減圧下(好ましくは減圧下)、30~100℃程度、好ましくは30~50℃程度の温度で行われる。
なお、一度、樹脂を析出させて、分離した後に、再び溶媒に溶解させ、上記樹脂が難溶或いは不溶の溶媒と接触させてもよい。即ち、上記ラジカル重合反応終了後、上記ポリマーが難溶或いは不溶の溶媒を接触させ、樹脂を析出させ(工程a)、樹脂を溶液から分離し(工程b)、改めて溶媒に溶解させ樹脂溶液Aを調製(工程c)、その後、上記樹脂溶液Aに、上記樹脂が難溶或いは不溶の溶媒を、樹脂溶液Aの10倍未満の体積量(好ましくは5倍以下の体積量)で、接触させることにより樹脂固体を析出させ(工程d)、析出した樹脂を分離する(工程e)ことを含む方法でもよい。
本発明の組成物に用いられる樹脂(B)の重量平均分子量は、GPC法によりポリスチレン換算値として、好ましくは1,000~200,000であり、より好ましくは2,000~100,000、さらにより好ましくは3,000~70,000、特に好ましくは5,000~50,000である。重量平均分子量を、1,000~200,000とすることにより、耐熱性やドライエッチング耐性の劣化を防ぐことができ、かつ現像性が劣化したり、粘度が高くなって製膜性が劣化することを防ぐことができる。
本発明の感活性光線性または感放射線性樹脂組成物において、樹脂(A)の組成物全体中の配合率は、全固形分中30~99質量%が好ましく、より好ましくは60~95質量%である。
また、本発明において、樹脂(B)は、1種で使用してもよいし、複数併用してもよい。
本発明で用いる感光性樹脂組成物は、架橋剤を含んでいても良い。架橋剤としては、酸存在下、加熱処理で架橋反応が起こるものであれば制限は無い。例えば、以下に述べる分子内に2個以上のエポキシ基またはオキセタニル基を有する化合物、アルコキシメチル基含有架橋剤、または、少なくとも1個のエチレン性不飽和二重結合を有する化合物を添加することができる。
これらの架橋剤の中で、分子内に2個以上のエポキシ基またはオキセタニル基を有する化合物が好ましく、エポキシ樹脂が特に好ましい。
分子内に2個以上のエポキシ基を有する化合物の具体例としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪族エポキシ樹脂等を挙げることができる。
その他にも、ADEKA RESIN EP-4000S、同EP-4003S、同EP-4010S、同EP-4011S(以上、(株)ADEKA製)、NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上、(株)ADEKA製)、デナコールEX-611、EX-612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、EX-321、EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX-832、EX-841、EX-911、EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-321L、EX-850L、DLC-201、DLC-203、DLC-204、DLC-205、DLC-206、DLC-301、DLC-402(以上ナガセケムテック製)、YH-300、YH-301、YH-302、YH-315、YH-324、YH-325(以上新日鐵化学製)などが挙げられる。
これらは1種単独または2種以上を組み合わせて使用することができる。
アルコキシメチル基含有架橋剤としては、ヒドロキシメチル基またはアルコキシメチル基を分子内に2個以上有する化合物を含むことが好ましい。
本発明の感活性光線性または感放射線性組成物は、パターン形状の観点から、架橋剤として、アルコキシメチル基を分子内に2個以上有する化合物を少なくとも2種含むことがより好ましく、アルコキシメチル基を分子内に2個以上有するフェノール化合物を少なくとも2種含むことがさらに好ましく、上記少なくとも2種のフェノール化合物の内の少なくとも1種が、分子内にベンゼン環を3~5個含み、さらにアルコキシメチル基を合わせて2個以上有し、分子量が1200以下のフェノール誘導体であることが特に好ましい。
アルコキシメチル基としては、メトキシメチル基、エトキシメチル基が好ましい。
このようにして合成されたフェノール誘導体のうち、アルコキシメチル基を有するフェノール誘導体が感度、保存安定性の点から特に好ましい。
これら架橋剤の中で特に好ましいものを以下に挙げる。
本発明で用いる感光性樹脂組成物は、(B)光酸発生剤との組み合わせにおいて、その分解を促進させるために、増感色素を含むことができる。特に、スルホニウムカチオンを有する化合物、ヨードニウムカチオンを有する化合物、ジアゾジスルホン化合物およびジスルホン化合物の少なくとも1種を用いる場合に、好ましく用いられる。
増感色素は、活性光線または放射線を吸収して電子励起状態となる。電子励起状態となった増感色素は、光酸発生剤と接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。
好ましい増感色素の例としては、以下の化合物類に属しており、かつ350nmから450nm域のいずれかに吸収波長を有する化合物を挙げることができる。
増感色素は、1種類のみ用いても良いし、2種類以上用いても良い。2種類以上用いる場合は、その合計量が上記範囲となる。増感色素の配合量は、光酸発生剤の0.1~20質量%であることが好ましく、1~10質量%であることがより好ましい。
本発明における感光性樹脂組成物は、溶剤を含むことが好ましい。
本発明における感光性樹脂組成物は、必須成分である特定樹脂および特定光酸発生剤、並びに、各種添加剤の任意成分を、溶剤に溶解した溶液として調製されることが好ましい。
また、これらの溶剤にさらに必要に応じて、ベンジルエチルエーテル、ジヘキシルエーテル、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、イソホロン、カプロン酸、カプリル酸、1-オクタノール、1-ノナール、ベンジルアルコール、アニソール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、炭酸エチレン、炭酸プロピレン等の溶剤を添加することもできる。
上記した溶剤のうち、プロピレングリコールモノアルキルエーテルアセテート類、および/または、ジエチレングリコールジアルキルエーテル類が好ましく、ジエチレングリコールエチルメチルエーテル、および/または、プロピレングリコールモノメチルエーテルアセテートが特に好ましい。
これら溶剤は、1種単独でまたは2種以上を混合して使用することができる。
溶剤は、1種類のみ用いても良く、2種類以上用いても良い。2種類以上用いる場合は、合計量が上記範囲となる。
塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、および、カルボン酸の第四級アンモニウム塩等が挙げられる。
芳香族アミンとしては、例えば、アニリン、ベンジルアミン、N,N-ジメチルアニリン、ジフェニルアミンなどが挙げられる。
複素環式アミンとしては、例えば、ピリジン、2-メチルピリジン、4-メチルピリジン、2-エチルピリジン、4-エチルピリジン、2-フェニルピリジン、4-本発明の感光性樹脂組成物は、(成分I)塩基性化合物を含むことが好ましい。
(成分I)塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、および、カルボン酸の第四級アンモニウム塩等が挙げられる。
芳香族アミンとしては、例えば、アニリン、ベンジルアミン、N,N-ジメチルアニリン、ジフェニルアミンなどが挙げられる。
複素環式アミンとしては、例えば、ピリジン、2-メチルピリジン、4-メチルピリジン、2-エチルピリジン、4-エチルピリジン、2-フェニルピリジン、4-フェニルピリジン、N-メチル-4-フェニルピリジン、4-ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、4-メチルイミダゾール、2-フェニルベンズイミダゾール、2,4,5-トリフェニルイミダゾール、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、8-オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、シクロヘキシルモルホリノエチルチオウレア、ピペラジン、モルホリン、4-メチルモルホリン、1,5-ジアザビシクロ[4.3.0]-5-ノネン、1,8-ジアザビシクロ[5.3.0]-7-ウンデセンなどが挙げられる。
カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ-n-ブチルアンモニウムアセテート、テトラ-n-ブチルアンモニウムベンゾエートなどが挙げられる。
本発明における感光性樹脂組成物が塩基性化合物を含む場合、塩基性化合物の含有量は、特定樹脂100重量部に対して、0.001~1重量部であることが好ましく、0.002~0.2重量部であることがより好ましい。
本発明で用いる感光性樹脂組成物は、塗布性をより向上させる観点から界面活性剤を含むことが好ましい。
界面活性剤としては、アニオン系、カチオン系、ノニオン系、または、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン系界面活性剤である。
ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、フッ素系、シリコーン系界面活性剤を挙げることができる。
これらのフッ素系界面活性剤、シリコーン系界面活性剤として、例えば、特開昭62-36663号、特開昭61-226746号、特開昭61-226745号、特開昭62-170950号、特開昭63-34540号、特開平7-230165号、特開平8-62834号、特開平9-54432号、特開平9-5988号、特開2001-330953号各公報記載の界面活性剤を挙げることができ、市販の界面活性剤を用いることもできる。
使用できる市販の界面活性剤として、例えば、エフトップEF301、EF303、(以上、新秋田化成(株)製)、フロラードFC430、431(以上、住友スリーエム(株)製)、メガファックF171、F173、F176、F189、R08(以上、DIC(株)製)、サーフロンS-382、SC101、102、103、104、105、106(以上、旭硝子(株)製)、PF-6320等のPolyFoxシリーズ(OMNOVA社製)等のフッ素系界面活性剤またはシリコーン系界面活性剤を挙げることができる。また、ポリシロキサンポリマーKP-341(信越化学工業(株)製)も、シリコーン系界面活性剤として用いることができる。
これら界面活性剤は、1種単独でまたは2種以上を混合して使用することができる。
本発明における感光性樹脂組成物が界面活性剤を含む場合、界面活性剤の添加量は、特定樹脂100重量部に対して、10重量部以下であることが好ましく、0.01~10重量部であることがより好ましく、0.01~1重量部であることがさらに好ましい。
<有機半導体膜のパターニング方法>
本発明における有機半導体膜のパターニング方法は、
(1)有機半導体膜の上に、保護膜を成膜する工程、
(2)保護膜の上記有機半導体膜と反対側の上に、pKaが-1以下の有機酸を発生する光酸発生剤を含む、感光性樹脂組成物からなるレジスト膜を成膜する工程、
(3)上記レジスト膜を露光する工程、
(4)有機溶剤を含む現像液を用いて現像しマスクパターンを作製する工程、
(5)ドライエッチング処理にて少なくとも非マスク部の上記保護膜および上記有機半導体膜を除去する工程、
(6)上記保護膜を水で溶解する工程、
を含むことを特徴とする。
本発明の有機半導体膜のパターニング方法は、有機半導体膜の上に保護膜を成膜する工程を含む。通常は、基板の上に有機半導体膜を製膜した後に、本工程を行う。この場合、保護膜は、有機半導体の基板側の面と反対側の面に成膜する。保護膜は、通常、有機半導体膜の表面に設けられるが、本発明の趣旨を逸脱しない範囲で他の層を設けてもよい。具体的には、水溶性の下塗り層等が挙げられる。また、保護膜は1枚のみ設けられていてもよいし、2枚以上設けられていてもよい。
上記(1)の工程後、(2)保護膜の有機半導体側の面と反対側の上に、感光性樹脂組成物からなるレジスト膜を形成する。レジスト膜は好ましくは保護膜の表面に感光性樹脂組成物を適用して形成されるが、下塗り層等の膜を介していてもよい。感光性樹脂組成物の適用方法は、上記保護膜の記載を参酌できる。
(2)工程でレジスト膜を成膜後、上記レジスト膜を露光する。具体的には、レジスト膜に所定のパターンを有するマスクを介して、活性光線を照射する。露光は1回のみ行ってもよく、複数回行ってもよい。
具体的には、感光性樹脂組成物の乾燥塗膜を設けた基板に所定のパターンの活性光線を照射する。露光はマスクを介して行ってもよいし、所定のパターンを直接描画してもよい。波長300nm以上450nm以下の波長、好ましくは365nmを有する活性光線が好ましく使用できる。この工程の後、必要に応じて露光後加熱工程(PEB)を行ってもよい。
水銀灯を用いる場合にはg線(436nm)、i線(365nm)、h線(405nm)などの波長を有する活性光線が好ましく使用できる。水銀灯はレーザに比べると、大面積の露光に適するという点で好ましい。
また、パルス幅は、0.1nsec以上30,000nsec以下であることが好ましい。アブレーション現象により色塗膜を分解させないようにするには、0.5nsec以上がより好ましく、1nsec以上が最も好ましく、スキャン露光の際に合わせ精度を向上させるには、1,000nsec以下がより好ましく、50nsec以下が最も好ましい。
さらに、レーザの周波数は、1Hz以上50,000Hz以下が好ましく、10Hz以上1,000Hz以下がより好ましい。
さらに、レーザの周波数は、露光処理時間を短くするには、10Hz以上がより好ましく、100Hz以上が最も好ましく、スキャン露光の際に合わせ精度を向上させるには、10,000Hz以下がより好ましく、1,000Hz以下が最も好ましい。
本発明に使用可能な露光装置としては、特に制限はないが市販されているものとしては、Callisto((株)ブイ・テクノロジー製)やAEGIS((株)ブイ・テクノロジー製)やDF2200G(大日本スクリーン製造(株)製)などが使用可能である。また上記以外の装置も好適に用いられる。
また、必要に応じて長波長カットフィルタ、短波長カットフィルタ、バンドパスフィルタのような分光フィルタを通して照射光を調整することもできる。
(3)工程でレジスト膜を露光後、有機溶剤を含む現像液を用いて現像する。現像はネガ型が好ましい。現像液に含まれる溶剤のsp値は、19MPa1/2未満であることが好ましく、18MPa1/2以下であることがより好ましい。
ケトン系溶剤としては、例えば、1-オクタノン、2-オクタノン、1-ノナノン、2-ノナノン、2-ヘプタノン(メチルアミルケトン)、4-ヘプタノン、1-ヘキサノン、2-ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトン、イソホロン、プロピレンカーボネート等を挙げることができる。
エステル系溶剤としては、例えば、酢酸メチル、酢酸ブチル、酢酸エチル、酢酸イソプロピル、酢酸ペンチル、酢酸イソペンチル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチル-3-エトキシプロピオネート、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル等を挙げることができる。
アミド系溶剤としては、例えば、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ヘキサメチルホスホリックトリアミド、1,3-ジメチル-2-イミダゾリジノン等が使用できる。
炭化水素系溶剤としては、例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、ペンタン、ヘキサン、オクタン、デカン等の脂肪族炭化水素系溶剤が挙げられる。
上記の溶剤は、1種類のみでも、2種以上用いてもよい。また、上記以外の溶剤と混合し使用してもよい。但し、本発明の効果を十二分に奏するためには、現像液全体としての含水率が10質量%未満であることが好ましく、実質的に水分を含有しないことがより好ましい。ここでの実質的とは、例えば、現像液全体としての含水率が3質量%以下であり、より好ましくは測定限界以下であることをいう。
すなわち、有機系現像液に対する有機溶剤の使用量は、現像液の全量に対して、90質量%以上100質量%以下であることが好ましく、95質量%以上100質量%以下であることが好ましい。
特に、有機系現像液は、ケトン系溶剤、エステル系溶剤およびアミド系溶剤からなる群より選択される少なくとも1種類の有機溶剤を含む現像液であるのが好ましい。
また、有機系現像液は、必要に応じて塩基性化合物を適当量含有していてもよい。塩基性化合物の例としては、塩基性化合物の項で前述したものを挙げることができる。
5kPa以下の蒸気圧を有する具体的な例としては、1-オクタノン、2-オクタノン、1-ノナノン、2-ノナノン、2-ヘプタノン(メチルアミルケトン)、4-ヘプタノン、2-ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン、メチルイソブチルケトン等のケトン系溶剤、酢酸ブチル、酢酸ペンチル、酢酸イソペンチル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチル-3-エトキシプロピオネート、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、蟻酸ブチル、蟻酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル等のエステル系溶剤、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミドのアミド系溶剤、トルエン、キシレン等の芳香族炭化水素系溶剤、オクタン、デカン等の脂肪族炭化水素系溶剤が挙げられる。
特に好ましい範囲である2kPa以下の蒸気圧を有する具体的な例としては、1-オクタノン、2-オクタノン、1-ノナノン、2-ノナノン、4-ヘプタノン、2-ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン等のケトン系溶剤、酢酸ブチル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチル-3-エトキシプロピオネート、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、乳酸エチル、乳酸ブチル、乳酸プロピル等のエステル系溶剤、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミドのアミド系溶剤、キシレン等の芳香族炭化水素系溶剤、オクタン、デカン等の脂肪族炭化水素系溶剤が挙げられる。
界面活性剤としては特に限定されないが、例えば、上記水溶性樹脂組成物の欄で述べた界面活性剤が好ましく用いられる。
現像液に界面化成剤を配合する場合、その配合量は現像液の全量に対して、通常0.001~5質量%、好ましくは0.005~2質量%、さらに好ましくは0.01~0.5質量%である。
上記各種の現像方法が、現像装置の現像ノズルから現像液をレジスト膜に向けて吐出する工程を含む場合、吐出される現像液の吐出圧(吐出される現像液の単位面積あたりの流速)は好ましくは2mL/sec/mm2以下、より好ましくは1.5mL/sec/mm2以下、さらに好ましくは1mL/sec/mm2以下である。流速の下限は特に無いが、スループットを考慮すると0.2mL/sec/mm2以上が好ましい。
吐出される現像液の吐出圧を上記の範囲とすることにより、現像後のレジスト残渣に由来するパターンの欠陥を著しく低減することができる。
このメカニズムの詳細は定かではないが、恐らくは、吐出圧を上記範囲とすることで、現像液がレジスト膜に与える圧力が小さくなり、レジスト膜・レジストパターンが不用意に削られたり崩れたりすることが抑制されるためと考えられる。
なお、現像液の吐出圧(mL/sec/mm2)は、現像装置中の現像ノズル出口における値である。
レジスト膜を現像しマスクパターンを作製後、エッチング処理にて少なくとも非マスク部の上記水溶性樹脂膜および上記有機半導体を除去する。非マスク部とは、レジスト膜を露光してマスクパターンを作製する際のマスクにより露光されていない箇所を表す。
フッ素系ガスと酸素ガス(O2)との混合ガスを用い、有機半導体が露出しない領域(深さ)までエッチングを行なう第1段階のエッチングと、この第1段階のエッチングの後に、窒素ガス(N2)と酸素ガス(O2)との混合ガスを用い、好ましくは有機半導体が露出する領域(深さ)付近までエッチングを行なう第2段階のエッチングと、有機半導体が露出した後に行なうオーバーエッチングとを含む形態が好ましい。以下、ドライエッチングの具体的手法、並びに第1段階のエッチング、第2段階のエッチング、およびオーバーエッチングについて説明する。
(1)第1段階のエッチングにおけるエッチングレート(nm/min)と、第2段階のエッチングにおけるエッチングレート(nm/min)とをそれぞれ算出する。(2)第1段階のエッチングで所望の厚さをエッチングする時間と、第2段階のエッチングで所望の厚さをエッチングする時間とをそれぞれ算出する。(3)上記(2)で算出したエッチング時間に従って第1段階のエッチングを実施する。(4)上記(2)で算出したエッチング時間に従って第2段階のエッチングを実施する。あるいはエンドポイント検出でエッチング時間を決定し、決定したエッチング時間に従って第2段階のエッチングを実施してもよい。(5)上記(3)、(4)の合計時間に対してオーバーエッチング時間を算出し、オーバーエッチングを実施する。
エッチング後、溶剤または水を用いて保護膜を除去する。水溶性樹脂の場合は、水が好ましい。
水溶性樹脂膜を水で除去する方法としては、例えば、スプレー式またはシャワー式の噴射ノズルからレジストパターンに洗浄水を噴射して、保護膜を除去する方法を挙げることができる。洗浄水としては、純水を好ましく用いることができる。また、噴射ノズルとしては、その噴射範囲内に支持体全体が包含される噴射ノズルや、可動式の噴射ノズルであってその可動範囲が支持体全体を包含する噴射ノズルを挙げることができる。噴射ノズルが可動式の場合、水溶性樹脂膜を除去する工程中に支持体中心部から支持体端部までを2回以上移動して洗浄水を噴射することで、より効果的にレジストパターンを除去することができる。
水を除去した後、乾燥等の工程を行うことも好ましい。乾燥温度としては、80~120℃とすることが好ましい。
本発明は、有機半導体を利用した電子デバイスの製造に用いることができる。ここで、電子デバイスとは、半導体を含有しかつ2つ以上の電極を有し、その電極間に流れる電流や生じる電圧を、電気、光、磁気、化学物質などにより制御するデバイス、あるいは、印加した電圧や電流により、光や電場、磁場などを発生させるデバイスである。例としては、有機光電変換素子、有機電界効果トランジスタ、有機電界発光素子、ガスセンサ、有機整流素子、有機インバータ、情報記録素子などが挙げられる。有機光電変換素子は光センサ用途、エネルギー変換用途(太陽電池)のいずれにも用いることができる。これらの中で、好ましくは有機電界効果トランジスタ、有機光電変換素子、有機電界発光素子であり、より好ましくは有機電界効果トランジスタ、有機光電変換素子であり、特に好ましくは有機電界効果トランジスタである。
THPMA:2-テトラヒドロピラニルメタクリレート(合成品)
V-601:2,2-アゾビス(2-メチルプロピオン酸)ジメチル(和光純薬工業(株)製)
PGMEA:メトキシプロピルアセテート(ダイセル化学工業(株)製)
3つ口フラスコにメタクリル酸50.33g(0.585mol)、カンファースルホン酸0.27g(0.2モル%)を混合して15℃に冷却した。その溶液に3,4-ジヒドロフラン49.21g(0.585mol)を滴下した。反応液に飽和炭酸水素ナトリウム水溶液(500mL)を加え、酢酸エチル(500mL)で抽出し、硫酸マグネシウムで乾燥した。不溶物をろ過後40℃以下で減圧濃縮し、残渣の無色油状物を減圧蒸留することで68.64gのTHPMAを得た。
3つ口フラスコにPGMEA(24.16g)を入れ、窒素雰囲気下において86℃に昇温した。その溶液にTHPMA(11.60g)、ノルボルナンラクトンメタクリレート(9.18g)、シクロヘキシルメタクリレート(3.38g)、V-601(0.895g、モノマーに対して2.59モル%)をPGMEA(16.10g)とγ―ブチルラクトン(8.05g)の混合溶液に溶解させ、3時間かけて滴下した。滴下終了後4時間撹拌し、反応を終了させた。反応液をメタノール2L中に再沈することで生じた白色粉体を濾過により回収することで樹脂B1を得た。重量平均分子量は21,000であった。
使用するモノマー以外は樹脂B1の合成例と同様にして、樹脂B2~B10を得た。
2-ナフトール(10g)、クロロベンゼン(30mL)の懸濁溶液に塩化アルミニウム(10.6g)、2-クロロプロピオニルクロリド(10.1g)を添加し、混合液を40℃に加熱して2時間反応させた。氷冷下、反応液に4N-HCl水溶液(60mL)を滴下し、酢酸エチル(50mL)を添加して分液した。有機層に炭酸カリウム(19.2g)を加え、40℃で1時間反応させた後、2N-HCl水溶液(60mL)を添加して分液し、有機層を濃縮後、結晶をジイソプロピルエーテル(10mL)でリスラリーし、ろ過、乾燥してケトン化合物(6.5g)を得た。
得られたケトン化合物(3.0g)、メタノール(30mL)の懸濁溶液に酢酸(7.3g)、50重量%ヒドロキシルアミン水溶液(8.0g)を添加し、加熱還流した。放冷後、水(50mL)を加え、析出した結晶をろ過、冷メタノール洗浄後、乾燥してオキシム化合物(2.4g)を得た。
得られたオキシム化合物(1.8g)をアセトン(20mL)に溶解させ、氷冷下トリエチルアミン(1.5g)、2,4、6-トリイソプロピルフェニルスルホニルクロリド(3.8g)を添加し、室温に昇温して1時間反応させた。反応液に水(50mL)を添加し、析出した結晶をろ過後、メタノール(20mL)でリスラリーし、ろ過、乾燥して光酸発生剤A1(2.3g)を得た。
N-ヒドロキシ-1,8-ナフタルイミド(10.65g)をDMF(100ml)に溶解させ、氷冷下トリエチルアミン(1.5g)、2,4、6-トリイソプロピルフェニルスルホニルクロリド(16.0g)を添加し、室温に昇温して1時間反応させた。反応液に水(500mL)を添加し、析出した結晶をろ過後、メタノール(20mL)でリスラリーし、ろ過、乾燥して光酸発生剤A2(19.7g)を得た。
2,4、6-トリイソプロピルフェニルスルホニルクロリド(16.0g)をメタノール100mlに溶解させたところにアンモニア水(28%溶液、3.3g)を添加して攪拌させた4-(フェニルチオ)フェニルジフェニルヨードニウムクロリド(20.6g)をメタノール100mlに溶解し、そこに上記の様にして調整した2,4、6-トリイソプロピルフェニルスルホン酸アンモニウム塩を加えて塩交換した。エバポレーターを用いて溶媒を減圧下除去した後、水-アセトン(8:2)の混合溶液で洗浄後再結晶して、光酸発生剤A6(23.5g)を得た。
2,4、6-トリイソプロピルシクロヘキシルフェニルスルホニルクロリド(16.0g)を2,4、6-トリシクロヘキシルフェニルスルホニルクロリド(23g)に変えた以外は、光酸発生剤A6の合成と同様にして光酸発生剤A7(25.7g)を得た。
ブロモメチルシクロヘキサン20g、1-ナフトール(12.5g)を三口フラスコ中でNMP300gに溶解させた後、炭酸カリウム(12g)、ヨウ化カリウム(14g)を加え120℃で8時間加熱した。反応液に水300gを加え、ヘキサン100gで3回抽出を行い、得られた有機層を合わせ、1N水酸化ナトリウム水溶液100gで1回、水100gで1回、Brine100gで1回洗浄した後、濃縮しシクロヘキシルメチルナフチルエーテルを13g得た。
13.1gのシクロヘキシルメチルナフチルエーテルを三口フラスコ中でEaton試薬65gに溶解させた後、攪拌しながらテトラメチレンスルホキシド5.7gを滴下し、さらに3時間攪拌を行った。反応液を、水240gにあけた後、2,4、6-トリシクロヘキシルフェニルスルホニルクロリド(23g)とクロロホルムを50g添加した。有機層を分離した後、水層からクロロホルム50gを用いてさらに2回抽出を行った。得られた有機層を合わせ、水洗を2回行い濃縮した。得られた組成生物を酢酸エチル20gを用いて再結晶を行い、光酸発生剤A8を22g得た。
ノナフロオロプロピル-1,3-ジスルホニルフルオライド(7.5g)をTHF(100ml)に溶解した後、1,3,5-トリシクロヘキシルフェノール(6.8g)を添加した。そこへトリエチルアミン(4.4g)を室温にて1時間かけて滴下した後、室温で6時間攪拌した。続いて、トリフルオロメタンスルホンアミド(3.0g)を添加し、反応液を1時間かけて80℃まで加熱し6時間攪拌した。反応液を室温まで冷却した後、酢酸エチル(300ml)を添加し、生じた沈殿を濾過により除去した。反応液を脱イオン水で分液洗浄したところにイソプロパノール(30ml)と1N塩酸(10ml)を加え、60℃で3時間加熱した後、室温まで冷却し、蒸留水1Lに晶析した。
得られた結晶をTHF(100ml)とIPA(30ml)の混合溶液に溶解させた後、ジ(4-t-ブチルフェニル)ヨードニウムブロマイド(3.5g)のTHF溶液を添加し塩交換した。塩化メチレン(100ml)で2回抽出した後、蒸留水(100ml)で5回洗浄し、濃縮した。得られたオイル状の粗生成物にシクロヘキシルメチルエーテルを50ml加えて攪拌し、析出した結晶を濾過する事により、光酸発生剤A10(3.9g)を得た。
下記表に示す各成分を溶剤F1(PGMEA)と共に混合して均一な溶液とした後、0.1μmのポアサイズを有するポリテトラフルオロエチレン製フィルタを用いてろ過して、実施例1~21および比較例1~12の保護膜形成用組成物および感光性樹脂組成物をそれぞれ調製した。固形分濃度は15質量%であった。
X1:ポリビニルピロリドン(ピッツコール K-30、第一工業製薬(株)製)
X2:ポリビニルアルコール(PXP-05、日本酢ビ・ポバール株(株)製)
X3:プルラン((株)林原製)
X4:メチルセルロース(メトローズ SM―4 信越化学工業(株)製)
Y1:サーフィノール440(日信化学工業(株)製)
A1:(下記構造、合成品)、発生酸のpKa-2
A2:(下記構造、合成品)、発生酸のpKa-2
A3:(下記構造、みどり化学(株)製)、発生酸のpKa-1
A4:(下記構造、和光純薬工業(株)製)、発生酸のpKa-2
A5:(下記構造、みどり化学(株)製)、発生酸のpKa-2
A6:(下記構造、合成品)、発生酸のpKa-2
A7:(下記構造、合成品)、発生酸のpKa-2
A8:(下記構造、合成品)、発生酸のpKa-2
A9:(下記構造、みどり化学(株)製)、発生酸のpKa-2
A10:(下記構造、合成品)
AC1:(下記構造)、発生酸(無機酸)のpKa-7
AC2:(下記構造)、発生酸(無機酸)のpKa-8
AC3:(下記構造)、発生酸のpKa-0.25
発生酸のpKaは、D.H. Ripin, D.A. Evans pKa Table pKa Data Compiled by R. Williamsに従って測定した。
B2:(下記構造、合成品)
B3:(下記構造、合成品)
B4:(下記構造、合成品)
B5:(下記構造、合成品)
B6:(下記構造、合成品)
B7:(下記構造、合成品)
B8:(下記構造、合成品)
B9:(下記構造、合成品)
B10:(下記構造、合成品)
B11:(下記構造、日本曹達(株)製)
C:シクロヘキシルモルホリノエチルチオウレア(下記構造、稲畑産業(株)製)
D1:ニカラックMX-270(下記構造、(株)三和ケミカル製)
D2:ニカラックMX-100LM(下記構造、(株)三和ケミカル製)
D3:セロキサイド2021P(下記構造、(株)ダイセル製)
D4:YX-4000H(下記構造、三菱化学(株)製)
G1:9,10-ジブトキシアントラセン(Aldrich社製)
E1:PF-6320(OMNOVA Solutions Inc.製)
F1:PGMEA メトキシプロピルアセテート(ダイセル化学工業(株)製)
B2:
B3:
B4:
B6:
B7:
B8:
B9:
B10:
B11:
有機半導体として濃度20g/LのP3HT(Merck社製)クロロベンゼン溶液10mLと濃度14g/Lの[60]PCBM(Solenne社製)クロロベンゼン溶液10mLとを混合し、4インチベアシリコン基板上にスピンコーター(1200rpm、30秒)にて塗布し、ホットプレートにて140℃/15分乾燥し、膜厚100nmの有機半導体膜を形成した。有機半導体膜を基板上に形成したウエハをウエハ1とした。ウエハ1上に表1に記載した保護膜形成用組成物をスピンコーター(1200rpm、30秒)により塗布したのち、100℃で60秒ベークし、有機半導体膜上に膜厚700nmの保護膜が設けられたウエハ2を形成した。
上記記載の4インチのウエハ2に下記表1に示す感光性樹脂組成物をスピンコーター(1200rpm,30秒)により塗布したのち、110℃で60秒ベークし、ウエハ2上に膜厚500nmのレジスト膜を形成したウエハ3を形成した。
次にウエハ3をi線投影露光装置NSR2005i9C(ニコン社製)で、NA:0.57、シグマ:0.60の光学条件にて露光(露光量120mJ/cm2)を行ない、線幅10μmの1:1ラインアンドスペースパターンのバイナリーマスクを通して露光した。その後110℃で、60秒間加熱した後、酢酸ブチルで15秒間現像し、スピン乾燥して線幅10μmの1:1ラインアンドスペースのレジストパターンを得た。走査型電子顕微鏡を用いて断面観察を行うことで感光性樹脂組成物のパターン形状と基板上(非パターン部)の残渣を評価した。
A:感光性樹脂組成物のボトム部分のアンダーカットがなく、パターンのテーパー角が85°~95°の範囲。
なく矩形プロファイル
B:感光性樹脂組成物のボトム部分にアンダーカットが0.5μm以下であり、パターンのテーパー角が85°~95°の範囲。
僅かに認められるが矩形プロファイル
C:感光性樹脂組成物のボトム部分にアンダーカットが0.5μm以下であり、パターンのテーパー角が95°~105°の範囲(逆テーパー)。
D:パターン形状劣悪もしくはパターン形成せず。
以下の条件で基板のドライエッチングを行い、非マスクパターン部の保護膜2および非マスクパターン部の有機半導体1を除去した。
ガス:CF4(流量200ml/min)、Ar(流量800ml/min)、O2(流量50ml/min)
ソースパワー:800W
ウェハバイアス:600W
アンテナバイアス:100W
ESC電圧:400V
時間:60sec
得られた基板を水洗し、保護膜からなるパターンを除去したのち、100℃で10分加熱し上記有機半導体1に残存する水分の除去と、乾燥によりプロセスにおけるダメージを修復することで、有機半導体膜がパターニングされた基板を得た。
ドライエッチングおよび、保護膜除去後の有機半導体のパターンを、走査型電子顕微鏡を用いて観察を行うことより有機半導体の線幅を評価した。
A:感光性樹脂組成物の10μm(L/Sパターン)下における有機半導体の線幅が9μm~10μm
B:感光性樹脂組成物の1μmのL/Sパターン下における、有機半導体の線幅が8μm以上9μm未満
C:感光性樹脂組成物の1μmのL/Sパターン下における、有機半導体の線幅が8μm未満
また、有機半導体パターンの加工後の線幅評価について、ドライエッチングガスの種類を塩素/Arに変更しても、同様の傾向が得られることを確認した。
本願発明を用いることで特開2012-216501号公報の図2に記載の表示装置を容易に製造することができる。
Claims (25)
- 有機半導体膜と、前記有機半導体膜上の保護膜と、前記保護膜上のレジスト膜を有し、前記レジスト膜が、発生酸のpKaが-1以下の有機酸を発生する光酸発生剤(A)と、前記光酸発生剤から生じる酸に反応して有機溶剤を含む現像液に対する溶解速度が減少する樹脂(B)を含む感光性樹脂組成物からなる積層体。
- 光酸発生剤(A)が、スルホン酸、トリアルキルスルホニルメチド酸およびジアルキルスルホニルイミド酸から選ばれる少なくとも1種を含む、請求項1に記載の積層体。
- 光酸発生剤(A)が、オキシムスルホネート基および/またはイミドスルホネート基を有する化合物を含む、請求項1または2に記載の積層体。
- 光酸発生剤(A)が、スルホニウムカチオンおよび/またはヨードニウムカチオンを有する化合物を含む、請求項1または2に記載の積層体。
- 光酸発生剤(A)が、ジアゾジスルホン化合物および/またはジスルホン化合物を含む、請求項1または2に記載の積層体。
- 保護膜が水溶性樹脂を含む、請求項1~5のいずれか1項に記載の積層体。
- 感光性樹脂組成物が、光酸発生剤(A)から生じる発生酸によって極性が変化し、有機溶剤を含む現像液に対する溶解速度が減少する、請求項1~6のいずれか1項に記載の積層体。
- 感光性樹脂組成物が、光酸発生剤(A)から生じる発生酸によって樹脂(B)に架橋反応が起こることで、有機溶剤を含む現像液に対する溶解速度が減少する、請求項1~7のいずれかに記載の積層体。
- 感光性樹脂組成物が、光酸発生剤(A)を分光増感する増感色素を含む、請求項1~8のいずれか1項に記載の積層体。
- 発生酸のpKaが-1以下の有機酸を発生する光酸発生剤(A)と、前記光酸発生剤から生じる酸に反応して有機溶剤を含む現像液に対する溶解速度が減少する樹脂(B)を含む、有機半導体製造用レジスト組成物と、水溶性樹脂を含む保護膜形成用組成物を含む、有機半導体製造用キット。
- 光酸発生剤(A)が、スルホン酸、トリアルキルスルホニルメチド酸およびジアルキルスルホニルイミド酸から選ばれる少なくとも1種を含む、請求項10に記載の有機半導体製造用キット。
- 光酸発生剤(A)が、オキシムスルホネート基および/またはイミドスルホネート基を有する化合物を含む、請求項10または11に記載の有機半導体製造用キット。
- 光酸発生剤(A)が、スルホニウムカチオンおよび/またはヨードニウムカチオンを有する化合物を含む、請求項10または11に記載の有機半導体製造用キット。
- 光酸発生剤(A)が、ジアゾジスルホン化合物および/またはジスルホン化合物を含む、請求項10または11に記載の有機半導体製造用キット。
- 前記有機半導体製造用レジスト組成物が、光酸発生剤(A)から生じる酸によって極性が変化し、有機溶剤を含む現像液に対する溶解速度が減少する、請求項10~14のいずれか1項に記載の有機半導体製造用キット。
- 感光性樹脂組成物が、光酸発生剤(A)から生じる酸によって樹脂(B)に架橋反応が起こることで、有機溶剤を含む現像液に対する溶解速度が減少する、請求項10~15のいずれか1項に記載の有機半導体製造用キット。
- さらに、光酸発生剤(A)を分光増感する増感色素を含む、請求項10~16のいずれか1項に記載の有機半導体製造用キット。
- 発生酸のpKaが-1以下の有機酸を発生する光酸発生剤(A)と、前記光酸発生剤から生じる酸に反応して有機溶剤を含む現像液に対する溶解速度が減少する樹脂(B)を含む、有機半導体製造用レジスト組成物。
- 光酸発生剤(A)が、スルホン酸、トリアルキルスルホニルメチド酸およびジアルキルスルホニルイミド酸から選ばれる少なくとも1種を含む、請求項18に記載の有機半導体製造用レジスト組成物。
- 光酸発生剤(A)が、オキシムスルホネート基および/またはイミドスルホネート基を有する化合物を含む、請求項18または19に記載の有機半導体製造用レジスト組成物。
- 光酸発生剤(A)が、スルホニウムカチオンおよび/またはヨードニウムカチオンを有する化合物を含む、請求項18または19に記載の有機半導体製造用レジスト組成物。
- 光酸発生剤(A)が、ジアゾジスルホン化合物および/またはジスルホン化合物を含む、請求項18または19に記載の有機半導体製造用レジスト組成物。
- 前記有機半導体製造用レジスト組成物が、光酸発生剤(A)から生じる酸によって極性が変化し、有機溶剤を含む現像液に対する溶解速度が減少する、請求項18~22のいずれか1項に記載の有機半導体製造用レジスト組成物。
- 感光性樹脂組成物が、光酸発生剤(A)から生じる酸によって樹脂(B)に架橋反応が起こることで、有機溶剤を含む現像液に対する溶解速度が減少する、請求項18~23のいずれか1項に記載の有機半導体製造用レジスト組成物。
- さらに、光酸発生剤(A)を分光増感する増感色素を含む、請求項18~24のいずれか1項に記載の有機半導体製造用レジスト組成物。
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Citations (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57148706A (en) | 1981-03-11 | 1982-09-14 | Canon Inc | Production of color filter |
JPS582809A (ja) | 1981-06-29 | 1983-01-08 | Nec Corp | カラ−フイルタ−の製造方法 |
JPS589108A (ja) | 1981-07-09 | 1983-01-19 | Canon Inc | カラ−フイルタ−の製造法 |
JPS5946628A (ja) | 1983-07-04 | 1984-03-16 | Canon Inc | カラ−表示素子 |
JPS59126506A (ja) | 1983-01-10 | 1984-07-21 | Canon Inc | カラ−フイルタ− |
EP0133216A1 (de) | 1983-07-11 | 1985-02-20 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung negativer Kopien mittels eines Materials auf Basis von 1,2-Chinondiaziden |
JPS6141102A (ja) | 1984-08-03 | 1986-02-27 | Canon Inc | 色分解フイルタ−の製造方法 |
JPS61226745A (ja) | 1985-03-30 | 1986-10-08 | Japan Synthetic Rubber Co Ltd | 半導体集積回路製造用のスピンコート用レジスト組成物 |
JPS61226746A (ja) | 1985-03-30 | 1986-10-08 | Japan Synthetic Rubber Co Ltd | 半導体集積回路製造用のスピンコート用レジスト組成物 |
JPS6236663A (ja) | 1985-08-12 | 1987-02-17 | Mitsubishi Chem Ind Ltd | ナフトキノンジアジド系化合物及び該化合物を含有するポジ型フオトレジスト組成物 |
EP0212482A2 (de) | 1985-08-12 | 1987-03-04 | Hoechst Celanese Corporation | Verfahren zur Herstellung negativer Bilder aus einem positiv arbeitenden Photoresist |
JPS62170950A (ja) | 1986-01-23 | 1987-07-28 | Fuji Photo Film Co Ltd | 感光性組成物 |
JPS6334540A (ja) | 1986-07-30 | 1988-02-15 | Mitsubishi Chem Ind Ltd | ポジ型フオトレジスト組成物 |
DE3634671A1 (de) | 1986-10-09 | 1988-05-19 | Hans Prof Dr Dr Kroeger | Antirheumatika mit verminderter toxizitaet |
DE3711264A1 (de) | 1987-04-03 | 1988-10-13 | Hoechst Ag | Lichtempfindliches gemisch und hieraus hergestelltes lichtempfindliches kopiermaterial |
JPH07230165A (ja) | 1993-06-30 | 1995-08-29 | Tokyo Ohka Kogyo Co Ltd | ポジ型ホトレジスト組成物 |
JPH0862834A (ja) | 1994-08-22 | 1996-03-08 | Mitsubishi Chem Corp | フォトレジスト組成物 |
JPH095988A (ja) | 1995-06-21 | 1997-01-10 | Mitsubishi Chem Corp | 感放射線性塗布組成物 |
JPH0954432A (ja) | 1995-08-18 | 1997-02-25 | Dainippon Ink & Chem Inc | フォトレジスト組成物 |
JP2001330953A (ja) | 2000-05-22 | 2001-11-30 | Jsr Corp | 感放射線性樹脂組成物 |
JP2003035948A (ja) | 2001-05-17 | 2003-02-07 | Fuji Photo Film Co Ltd | ポジ型感放射線性組成物 |
US20030077540A1 (en) | 2001-05-22 | 2003-04-24 | Fuji Photo Film Co., Ltd. | Positive photosensitive composition |
US20030224288A1 (en) | 2002-04-10 | 2003-12-04 | Fuji Photo Film Co., Ltd. | Stimulation sensitive composition and compound |
JP2004233661A (ja) | 2003-01-30 | 2004-08-19 | Fuji Photo Film Co Ltd | 感刺激性組成物及び化合物 |
JP2004240213A (ja) * | 2003-02-06 | 2004-08-26 | Rohm & Haas Electronic Materials Llc | フェノール−ビフェニレン樹脂を含むネガ型感光性樹脂組成物 |
JP2006041317A (ja) | 2004-07-29 | 2006-02-09 | Sony Corp | 有機半導体パターン及び有機半導体層のパターニング方法、有機半導体装置及びその製造方法、並びに表示装置 |
JP4168443B2 (ja) | 2003-07-30 | 2008-10-22 | Jsr株式会社 | 感放射線性樹脂組成物、層間絶縁膜およびマイクロレンズ、ならびにそれらの製造方法 |
JP2009037108A (ja) | 2007-08-03 | 2009-02-19 | Daicel Chem Ind Ltd | フォトレジスト用樹脂溶液の製造方法、フォトレジスト組成物およびパターン形成方法 |
WO2011122336A1 (ja) | 2010-03-30 | 2011-10-06 | Jsr株式会社 | 感放射線性樹脂組成物およびパターン形成方法 |
JP2011197587A (ja) * | 2010-03-23 | 2011-10-06 | Fujifilm Corp | パターン形成方法、化学増幅型レジスト組成物、及び、レジスト膜 |
JP2011209692A (ja) | 2010-03-11 | 2011-10-20 | Fujifilm Corp | ポジ型感光性樹脂組成物、硬化膜の形成方法、硬化膜、液晶表示装置、及び、有機el表示装置 |
JP2011215590A (ja) | 2010-01-20 | 2011-10-27 | Fujifilm Corp | 硬化膜の製造方法、感光性樹脂組成物、硬化膜、有機el表示装置、及び、液晶表示装置 |
JP2011254091A (ja) * | 2011-07-25 | 2011-12-15 | Sony Corp | 有機半導体装置及びその製造方法 |
JP2012505926A (ja) * | 2008-10-20 | 2012-03-08 | ビーエーエスエフ ソシエタス・ヨーロピア | スルホニウム誘導体および潜在酸としてのその使用 |
JP2012216501A (ja) | 2011-03-30 | 2012-11-08 | Canon Inc | 有機el表示装置の製造方法 |
JP2013047783A (ja) * | 2011-07-28 | 2013-03-07 | Fujifilm Corp | パターン形成方法、感活性光線性又は感放射線性樹脂組成物、レジスト膜、電子デバイスの製造方法、及び、電子デバイス |
JP2013145255A (ja) * | 2012-01-13 | 2013-07-25 | Shin Etsu Chem Co Ltd | パターン形成方法及びレジスト組成物 |
JP2013214053A (ja) | 2012-03-05 | 2013-10-17 | Fujifilm Corp | 感活性光線性又は感放射線性樹脂組成物、これを用いた感活性光線性又は感放射線性膜、及び、パターン形成方法 |
WO2014061708A1 (ja) * | 2012-10-19 | 2014-04-24 | 富士フイルム株式会社 | 保護膜形成用の樹脂組成物、保護膜、パターン形成方法、電子デバイスの製造方法及び電子デバイス |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1757124B (zh) * | 2003-03-07 | 2010-06-16 | 皇家飞利浦电子股份有限公司 | 制造电子装置的方法 |
JP2008286924A (ja) * | 2007-05-16 | 2008-11-27 | Panasonic Corp | 化学増幅型レジスト材料、トップコート膜形成用材料及びそれらを用いたパターン形成方法 |
KR101482652B1 (ko) | 2007-06-07 | 2015-01-16 | 주식회사 동진쎄미켐 | 유기반도체 보호막 조성물 |
JP5485198B2 (ja) * | 2011-02-21 | 2014-05-07 | 信越化学工業株式会社 | レジスト組成物及びこれを用いたパターン形成方法 |
JP2013068646A (ja) * | 2011-09-20 | 2013-04-18 | Tokyo Ohka Kogyo Co Ltd | レジスト組成物、レジストパターン形成方法 |
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-
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Patent Citations (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57148706A (en) | 1981-03-11 | 1982-09-14 | Canon Inc | Production of color filter |
JPS582809A (ja) | 1981-06-29 | 1983-01-08 | Nec Corp | カラ−フイルタ−の製造方法 |
JPS589108A (ja) | 1981-07-09 | 1983-01-19 | Canon Inc | カラ−フイルタ−の製造法 |
JPS59126506A (ja) | 1983-01-10 | 1984-07-21 | Canon Inc | カラ−フイルタ− |
JPS5946628A (ja) | 1983-07-04 | 1984-03-16 | Canon Inc | カラ−表示素子 |
EP0133216A1 (de) | 1983-07-11 | 1985-02-20 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung negativer Kopien mittels eines Materials auf Basis von 1,2-Chinondiaziden |
JPS6141102A (ja) | 1984-08-03 | 1986-02-27 | Canon Inc | 色分解フイルタ−の製造方法 |
JPS61226746A (ja) | 1985-03-30 | 1986-10-08 | Japan Synthetic Rubber Co Ltd | 半導体集積回路製造用のスピンコート用レジスト組成物 |
JPS61226745A (ja) | 1985-03-30 | 1986-10-08 | Japan Synthetic Rubber Co Ltd | 半導体集積回路製造用のスピンコート用レジスト組成物 |
JPS6236663A (ja) | 1985-08-12 | 1987-02-17 | Mitsubishi Chem Ind Ltd | ナフトキノンジアジド系化合物及び該化合物を含有するポジ型フオトレジスト組成物 |
EP0212482A2 (de) | 1985-08-12 | 1987-03-04 | Hoechst Celanese Corporation | Verfahren zur Herstellung negativer Bilder aus einem positiv arbeitenden Photoresist |
JPS62170950A (ja) | 1986-01-23 | 1987-07-28 | Fuji Photo Film Co Ltd | 感光性組成物 |
JPS6334540A (ja) | 1986-07-30 | 1988-02-15 | Mitsubishi Chem Ind Ltd | ポジ型フオトレジスト組成物 |
DE3634671A1 (de) | 1986-10-09 | 1988-05-19 | Hans Prof Dr Dr Kroeger | Antirheumatika mit verminderter toxizitaet |
DE3711264A1 (de) | 1987-04-03 | 1988-10-13 | Hoechst Ag | Lichtempfindliches gemisch und hieraus hergestelltes lichtempfindliches kopiermaterial |
JPH07230165A (ja) | 1993-06-30 | 1995-08-29 | Tokyo Ohka Kogyo Co Ltd | ポジ型ホトレジスト組成物 |
JPH0862834A (ja) | 1994-08-22 | 1996-03-08 | Mitsubishi Chem Corp | フォトレジスト組成物 |
JPH095988A (ja) | 1995-06-21 | 1997-01-10 | Mitsubishi Chem Corp | 感放射線性塗布組成物 |
JPH0954432A (ja) | 1995-08-18 | 1997-02-25 | Dainippon Ink & Chem Inc | フォトレジスト組成物 |
JP2001330953A (ja) | 2000-05-22 | 2001-11-30 | Jsr Corp | 感放射線性樹脂組成物 |
JP2003035948A (ja) | 2001-05-17 | 2003-02-07 | Fuji Photo Film Co Ltd | ポジ型感放射線性組成物 |
US20030077540A1 (en) | 2001-05-22 | 2003-04-24 | Fuji Photo Film Co., Ltd. | Positive photosensitive composition |
US20030224288A1 (en) | 2002-04-10 | 2003-12-04 | Fuji Photo Film Co., Ltd. | Stimulation sensitive composition and compound |
JP2004233661A (ja) | 2003-01-30 | 2004-08-19 | Fuji Photo Film Co Ltd | 感刺激性組成物及び化合物 |
JP2004240213A (ja) * | 2003-02-06 | 2004-08-26 | Rohm & Haas Electronic Materials Llc | フェノール−ビフェニレン樹脂を含むネガ型感光性樹脂組成物 |
JP4168443B2 (ja) | 2003-07-30 | 2008-10-22 | Jsr株式会社 | 感放射線性樹脂組成物、層間絶縁膜およびマイクロレンズ、ならびにそれらの製造方法 |
JP2006041317A (ja) | 2004-07-29 | 2006-02-09 | Sony Corp | 有機半導体パターン及び有機半導体層のパターニング方法、有機半導体装置及びその製造方法、並びに表示装置 |
JP2009037108A (ja) | 2007-08-03 | 2009-02-19 | Daicel Chem Ind Ltd | フォトレジスト用樹脂溶液の製造方法、フォトレジスト組成物およびパターン形成方法 |
JP2012505926A (ja) * | 2008-10-20 | 2012-03-08 | ビーエーエスエフ ソシエタス・ヨーロピア | スルホニウム誘導体および潜在酸としてのその使用 |
JP2011215590A (ja) | 2010-01-20 | 2011-10-27 | Fujifilm Corp | 硬化膜の製造方法、感光性樹脂組成物、硬化膜、有機el表示装置、及び、液晶表示装置 |
JP2011209692A (ja) | 2010-03-11 | 2011-10-20 | Fujifilm Corp | ポジ型感光性樹脂組成物、硬化膜の形成方法、硬化膜、液晶表示装置、及び、有機el表示装置 |
JP2011197587A (ja) * | 2010-03-23 | 2011-10-06 | Fujifilm Corp | パターン形成方法、化学増幅型レジスト組成物、及び、レジスト膜 |
WO2011122336A1 (ja) | 2010-03-30 | 2011-10-06 | Jsr株式会社 | 感放射線性樹脂組成物およびパターン形成方法 |
JP2012216501A (ja) | 2011-03-30 | 2012-11-08 | Canon Inc | 有機el表示装置の製造方法 |
JP2011254091A (ja) * | 2011-07-25 | 2011-12-15 | Sony Corp | 有機半導体装置及びその製造方法 |
JP2013047783A (ja) * | 2011-07-28 | 2013-03-07 | Fujifilm Corp | パターン形成方法、感活性光線性又は感放射線性樹脂組成物、レジスト膜、電子デバイスの製造方法、及び、電子デバイス |
JP2013145255A (ja) * | 2012-01-13 | 2013-07-25 | Shin Etsu Chem Co Ltd | パターン形成方法及びレジスト組成物 |
JP2013214053A (ja) | 2012-03-05 | 2013-10-17 | Fujifilm Corp | 感活性光線性又は感放射線性樹脂組成物、これを用いた感活性光線性又は感放射線性膜、及び、パターン形成方法 |
WO2014061708A1 (ja) * | 2012-10-19 | 2014-04-24 | 富士フイルム株式会社 | 保護膜形成用の樹脂組成物、保護膜、パターン形成方法、電子デバイスの製造方法及び電子デバイス |
Non-Patent Citations (1)
Title |
---|
See also references of EP3064997A4 |
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CN105683835B (zh) | 2019-11-26 |
EP3064997A4 (en) | 2016-11-23 |
US9929376B2 (en) | 2018-03-27 |
TW201523136A (zh) | 2015-06-16 |
TWI628510B (zh) | 2018-07-01 |
CN105683835A (zh) | 2016-06-15 |
EP3064997B1 (en) | 2021-04-28 |
KR20170139693A (ko) | 2017-12-19 |
KR101841992B1 (ko) | 2018-03-26 |
KR20160064167A (ko) | 2016-06-07 |
JP2015087609A (ja) | 2015-05-07 |
US20160240816A1 (en) | 2016-08-18 |
EP3064997A1 (en) | 2016-09-07 |
KR101824942B1 (ko) | 2018-02-02 |
JP6167016B2 (ja) | 2017-07-19 |
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