CN111819494A

CN111819494A - Photosensitive layer, laminate, photosensitive resin composition, and kit

Info

Publication number: CN111819494A
Application number: CN201980015313.5A
Authority: CN
Inventors: 增田诚也
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2018-02-26
Filing date: 2019-02-22
Publication date: 2020-10-23
Also published as: JPWO2019163951A1; TW201936396A; KR20200110425A; WO2019163951A1

Abstract

The invention provides a photosensitive layer, a laminate, a photosensitive resin composition and a kit, wherein the photosensitive layer is contained in the laminate having a water-soluble resin layer and the photosensitive layer, the photosensitive layer is formed by the photosensitive resin composition, the photosensitive resin composition comprises a compound generating acid by activating light or radiation irradiation and a resin generating change of dissolution speed of butyl acetate by the action of acid, the resin generating change of dissolution speed of butyl acetate by the action of acid is a hydrophobic resin soluble in butyl acetate at 23 ℃, the weight average molecular weight of the resin is 10,000-50,000, 50 mol% to 100 mol% of all structural units are protected by a hydrophobic protecting group, the dissolution speed when the photosensitive layer which is not irradiated is immersed in butyl acetate at 23 ℃ is more than 20nm/s and less than 200nm/s, the static contact angle of the photosensitive resin composition on the water-soluble resin layer is 60 DEG or less.

Description

Photosensitive layer, laminate, photosensitive resin composition, and kit

Technical Field

The invention relates to a photosensitive layer, a laminated body, a photosensitive resin composition and a kit.

Background

In recent years, electronic devices using organic semiconductors have been widely used. A device using an organic semiconductor has an advantage that it can be manufactured by a simple process, compared with a conventional device using an inorganic semiconductor such as silicon. Further, the organic semiconductor can easily change material characteristics by changing its molecular structure. Further, the material is widely varied, and it is considered that functions and elements which cannot be realized by an inorganic semiconductor can be realized. Organic semiconductors are applicable to electronic devices such as organic solar cells, organic electroluminescent displays, organic photodetectors, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifier elements, organic inverters, and information recording elements.

Patterning of organic semiconductors has been performed so far by printing techniques. However, there is a limit to microfabrication of a pattern formed by a printing technique. Also, the organic semiconductor has a problem of being easily damaged.

Therefore, a method of forming a pattern of an organic semiconductor using a water-soluble resin as a protective film is being studied. For example, patent document 1 discloses a laminate in which a specific water-soluble resin layer and a photosensitive layer are sequentially contained on an organic semiconductor layer, and the water-soluble resin layer is in contact with the photosensitive layer. This describes that the laminated body can be prevented from cracking while realizing a fine pattern by exposure and development of the photosensitive layer.

Patent documents

2 and 3 disclose a laminate having a water-soluble resin layer and a photosensitive layer on a surface of an organic semiconductor layer, in which a specific photoacid generator and a specific resin are blended in the photosensitive resin composition. This means that a good pattern can be formed on the organic semiconductor.

Prior art documents

Patent document

Patent document 1: international publication WO2016/175220 pamphlet

Patent document 2: japanese laid-open patent publication (Kokai) No. 2015-194674

Patent document 3: japanese laid-open patent publication (JP 2015-087609)

Disclosure of Invention

Technical problem to be solved by the invention

According to the above-described technique, the water-soluble resin layer is interposed between the organic semiconductor layer and the photosensitive layer, whereby the protection of the organic semiconductor layer can be ensured.

In the case of producing a thick photosensitive layer, it is required to use a resin having a large molecular weight in the photosensitive layer. This is to suppress the generation of the dent. In addition, when pattern formation is performed a plurality of times, a thick photosensitive layer is required to suppress the influence of the step.

However, the resin having a large molecular weight causes a remarkably slow dissolution rate of the hydrophobic developing solution. Therefore, from the viewpoint of production efficiency, it is required to increase the dissolution rate. In order to increase the dissolution rate, it is conceivable to increase the hydrophobicity of the resin of the photosensitive layer, but in that case, the adhesion between the photosensitive layer and the water-soluble resin layer is reduced, causing pattern peeling or the like. The present invention has been made to solve the above problems, and an object of the present invention is to provide a photosensitive layer, a laminate, a photosensitive resin composition, and a kit, which can form a pattern appropriately even when a resin having a large molecular weight is used for the photosensitive layer.

Means for solving the technical problem

In order to solve the above problems, the present inventors have repeatedly conducted studies, improvements, and tests on various materials and structures. As a result, it was found that by designing the dissolution rate of the photosensitive layer and the static contact angle between the photosensitive resin composition and the water-soluble resin layer in a well-balanced manner, even when a resin having a large molecular weight is used for the photosensitive layer, a pattern can be appropriately formed, and the present invention was completed. Namely, the present invention provides the following embodiments.

[1] A photosensitive layer contained in a laminate having a water-soluble resin layer and a photosensitive layer,

the photosensitive layer is formed of a photosensitive resin composition containing a compound which generates an acid by irradiation of an activating light ray or a radiation ray and a resin which changes the dissolution rate of butyl acetate by the action of an acid, the resin which changes the dissolution rate of butyl acetate by the action of the acid is a hydrophobic resin which is soluble in butyl acetate at 23 ℃, the resin has a weight average molecular weight of 10,000 to 50,000, and 50 to 100 mol% of groups soluble in an alkali aqueous solution among all the structural units are protected by a hydrophobic protecting group,

the dissolution rate when the photosensitive layer is immersed in butyl acetate at 23 ℃ without irradiation is 20nm/s to 200nm/s,

the static contact angle of the photosensitive resin composition on the water-soluble resin layer is 60 DEG or less.

[2] The photosensitive layer according to [1], wherein the photosensitive layer has a photosensitivity to i-ray irradiation.

[3] The photosensitive layer according to [1] or [2], wherein the content of water in the photosensitive resin composition is 0.01% by mass or more and 1% by mass or less.

[4] The photosensitive layer according to any one of [1] to [3], wherein the change in the dissolution rate is a decrease in the dissolution rate.

[5] The photosensitive layer according to any one of [1] to [4], wherein the resin contained in the photosensitive layer has a structural unit represented by the following formula (1),

[ chemical formula 1]

In the formula, R⁸Represents a hydrogen atom or an alkyl group, L¹Represents a carbonyl group or a phenylene group, R¹～R⁷Each independently represents a hydrogen atom or an alkyl group.

[6] The photosensitive layer according to any one of [1] to [5], wherein the photosensitive resin composition has a total content of sodium ions, potassium ions, and calcium ions of 1 mass ppt to 1000 mass ppb.

[7] A photosensitive layer according to any one of [1] to [6], which is used for organic semiconductor layer processing.

[8] A laminate having the photosensitive layer described in any one of [1] to [7] and a water-soluble resin layer.

[9] The laminate according to [8], further comprising an organic semiconductor layer, wherein the organic semiconductor layer, the water-soluble resin layer and the photosensitive layer are sequentially laminated.

[10] The laminate according to [8] or [9], wherein the resin in which the dissolution rate of butyl acetate changes due to the action of the acid is a mixture of a resin having a high dissolution rate of butyl acetate and a resin having a low dissolution rate of butyl acetate.

[11] A photosensitive resin composition for forming a photosensitive layer, wherein,

the photosensitive layer is a layer which is combined with a water-soluble resin layer to form a laminate, and the dissolution rate when the unexposed photosensitive layer is immersed in butyl acetate is 20nm/s to 200nm/s,

the photosensitive resin composition contains a compound which generates an acid by irradiation of an activating light or a radiation ray and a resin which changes the dissolution rate of butyl acetate by the action of the acid,

the resin whose dissolution rate of butyl acetate is changed by the action of the acid is a hydrophobic resin soluble in butyl acetate, has a weight average molecular weight of 10,000 to 50,000, is protected from 50 to 100 mol% of all the structural units with a hydrophobic protective group, is soluble in an aqueous alkali solution, and has a static contact angle of 60 DEG or less on the water-soluble resin layer.

[12] The photosensitive resin composition according to [11], which is used for processing an organic semiconductor layer.

[13] A kit for forming a water-soluble resin layer and a photosensitive layer in this order, the kit having the photosensitive resin composition according to [11] or [12] and a water-soluble resin composition.

[14 ] A kit according to [13] for use in organic semiconductor layer processing.

Effects of the invention

According to the present invention, it is possible to provide a laminate of photosensitive layers, a photosensitive resin composition, and a kit, which can suitably form a pattern even when a resin having a large molecular weight is used for the photosensitive layer.

Drawings

Fig. 1 is a cross-sectional view schematically showing the process of exposing and developing a photosensitive layer according to a preferred embodiment of the present invention, wherein (a) is a state before development and (b) is a state after development.

Detailed Description

The following description of the constituent elements of the present invention may be made based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the labels of the groups (atomic groups) in the present specification, the labels not labeled with substitution and unsubstituted include groups having no substituent and groups having a substituent. For example, the term "alkyl group" encompasses not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "activation light" as used herein refers to, for example, far ultraviolet rays typified by a bright line spectrum of a mercury lamp or an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In the present invention, "light" means an activating ray or a radiation ray. In the present specification, the term "exposure" includes, unless otherwise specified, not only exposure by far ultraviolet rays such as a mercury lamp and an excimer laser, an X-ray, and an EUV light, but also drawing by a particle beam such as an electron beam and an ion beam.

In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the lower limit value and the upper limit value.

In the present specification, "(meth) acrylate" represents both or either of acrylate and methacrylate, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acryloyl group" represents both or either of acryloyl group and methacryloyl group.

In the present specification, the term "step" means not only an independent step, but also a step that is not clearly distinguished from other steps, if the desired action of the step is achieved.

In the present specification, the solid content concentration means a percentage of the mass of the other components except the solvent with respect to the total mass of the composition.

In the present specification, the terms "upper" and "lower" may be used above or below the structure. That is, other structures may be inserted without contacting them. Unless otherwise specified, the photosensitive layer side is referred to as "upper" and the substrate or organic semiconductor layer side is referred to as "lower".

The photosensitive layer of the present invention is contained in a laminate comprising a water-soluble resin layer and a photosensitive layer, and is characterized in that, which is formed from a photosensitive resin composition containing a compound that generates an acid by irradiation of an activating light or radiation (this compound is sometimes referred to as an "acid generator" in the present specification) and a hydrophobic resin soluble in butyl acetate, the resin is a resin (acid-reactive resin) which produces a change in the dissolution rate of butyl acetate by the action of an acid, and has a weight-average molecular weight of 10,000 to 50,000, and 50 to 100 mol% of all structural units of groups soluble in an aqueous alkali solution are protected by a hydrophobic protective group, and the dissolution rate when the unexposed photosensitive layer is immersed in butyl acetate at 23 ℃ is 20 nm/sec or more and 200 nm/sec or less, the static contact angle of the composition for forming a photosensitive layer on the water-soluble resin layer is 60 ° or less.

With this configuration, even when a resin having a large molecular weight is used for the photosensitive layer, a pattern can be formed appropriately.

That is, the resin having a large molecular weight causes a remarkably slow dissolution rate in a hydrophobic developing solution. In order to increase the dissolution rate, it is conceivable to increase the hydrophobicity of the resin, but in that case, the adhesion to the water-soluble resin layer is reduced, and pattern peeling or the like occurs. Here, in order to suppress pattern peeling, it is considered that the pattern is adjusted so as not to include air bubbles or the like which easily causes pattern peeling. Therefore, by adjusting the contact angle between the photosensitive resin composition and the water-soluble resin layer within a predetermined range, a pattern can be successfully and appropriately formed even when a resin having a large molecular weight is used.

The photosensitive layer of the present invention is used in combination with a water-soluble resin layer, and preferably, both are disposed in a state of contact. In the embodiment of the present invention, the organic semiconductor layer 3 is disposed on the substrate 4 as in the example shown in fig. 1 (a). Further, a water-soluble resin layer 2 for protecting the organic semiconductor layer 3 is provided in contact with the organic semiconductor layer 3. Next, a photosensitive layer 1 is disposed on the water-soluble resin layer so as to be in contact with the water-soluble resin layer. In the example shown in fig. 1(b), the improved photosensitive layer 1 is formed, and even if it is exposed and developed through a predetermined mask, no defect is generated in the removing portion 5. As described above, the photosensitive layer of the present invention exhibits particularly high effects in a state of being laminated on a water-soluble resin layer.

Although fig. 1 shows an example of the form of the organic semiconductor layer, a water-soluble resin layer and a photosensitive layer may be used in combination on the surface of another material. In the present invention, it is preferably used for the organic semiconductor layer.

The laminate of the present invention is a laminate comprising the photosensitive layer of the present invention and a water-soluble resin layer, and preferably further comprises an organic semiconductor layer, wherein the organic semiconductor layer, the water-soluble resin layer and the photosensitive layer are sequentially laminated. Also, it is preferable that these layers contact each other.

The features of each layer, the materials constituting each layer, and the like will be described below.

< organic semiconductor layer >

The organic semiconductor layer is a layer containing an organic material showing the characteristics of a semiconductor. As in the case of a semiconductor made of an inorganic material, an organic semiconductor includes a p-type organic semiconductor which conducts with holes as carriers and an n-type organic semiconductor which conducts with electrons as carriers. The ease of flow of carriers in the organic semiconductor layer is represented by the carrier mobility μ. Although it depends on the application, generally, it is preferable that the mobility is high, preferably 10^-7cm²More preferably 10 or more,/Vs^-6cm²More preferably 10 or more/Vs^-5cm²Over Vs. The mobility can be determined by characteristics when a Field Effect Transistor (FET) element is manufactured or a time of flight (TOF) method.

As described above, the organic semiconductor layer is preferably formed on a substrate and used. That is, the organic semiconductor layer preferably has a substrate on the surface on the side away from the water-soluble resin layer.

Examples of the substrate include various materials such as silicon, quartz, ceramics, glass, polyester films such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), and polyimide films, and any substrate can be selected depending on the application. For example, in the case of using for a flexible element, a flexible substrate can be used. The thickness of the substrate is not particularly limited.

As the P-type semiconductor material that can be used in the organic semiconductor layer, any of organic semiconductor materials can be used as long as it shows a hole (hole) transport property, but P-type pi conjugated polymers (for example, substituted or unsubstituted polythiophenes (for example, poly (3-hexylthiophene) (P3HT, manufactured by Sigma-Aldrich co. llc)) polyselenophene, polypyrrole, polyparaphenylene vinylene, polythienylene vinylene, polyaniline and the like), condensed polycyclic compounds (for example, substituted or unsubstituted anthracene, tetracene, pentacene, anthracenedithiophene (anthaditophene), hexacenzocoronene and the like), triarylamine compounds (for example, m-MTDATA (4,4 ', 4 ″ -Tris [ (3-methylphenyl) anilino ] triphenylamine (4, 4', 4 ″ -Tris [ (3-methylienyl) phenylamine ] triphenylamine)), (for example, P-type pi conjugated polymers (for example, poly (3-hexylthiophene) (P3-cyclohexylthiophene, poly) (P-phenylene), polyaniline, and the like)) are preferable, 2-TNATA (4,4 '-Tris [2-naphthyl (phenyl) amino ] triphenylamine (4, 4' -Tris [2-naphthyl (phenyl) amino ] triphenylamine)), NPD (N, N '-bis [ (1-naphthyl) -N, N' -Diphenyl ] -1,1 '-biphenyl) -4, 4' -diamine (N, N '-Di [ (1-naphthyl) -N, N' -Diphenyl ] -1,1 '-biphenyl) -4, 4' -diamine)), TPD (N, N '-Diphenyl-N, N' -Di (m-tolyl) benzidine), mCP (1,3-bis (9-carbazolyl) benzene (1), 3-bis (9-carbazolyl) benzene)), CBP (4,4 '-bis (9-carbazolyl) -2, 2' -biphenyl)), hetero 5-membered ring compound (e.g., substituted or unsubstituted oligothiophene, TTF (tetrathiafulvalene), etc.), phthalocyanine compound (substituted or unsubstituted phthalocyanine of various central metals, naphthalocyanine, anthraphthalocyanine, tetrapyrazinyltetraazaporphyrin), porphyrin compound (substituted or unsubstituted porphyrin of various central metals), carbon nanotube in which a semiconductor polymer is modified, graphene, more preferably p-type pi-conjugated polymer, condensed polycyclic compound, triarylamine compound, hetero 5-membered ring compound, phthalocyanin compound, porphyrin compound, more preferably, the p-type pi conjugated polymer is used.

The n-type semiconductor material that can be used in the organic semiconductor layer may be any of organic semiconductor materials as long as it has an electron-transporting property, but is preferably a fullerene compound, an electron-deficient phthalocyanine compound, a naphthalene tetracarbonyl compound, a perylene tetracarbonyl compound, a TCNQ compound (tetracyanoquinodimethane compound), or an n-type pi-conjugated polymer, more preferably a fullerene compound, an electron-deficient phthalocyanine compound, a naphthalene tetracarbonyl compound, a perylene tetracarbonyl compound, or an n-type pi-conjugated polymer, and particularly preferably a fullerene compound or an n-type pi-conjugated polymer. In the present invention, the fullerene compound means a substituted or unsubstituted fullerene, and the fullerene may be C₆₀、C₇₀、C₇₆、C₇₈、C₈₀、C₈₂、C₈₄、C₈₆、C₈₈、C₉₀、C₉₆、C₁₁₆、C₁₈₀、C₂₄₀、C₅₄₀Of fullerenes and the likeEither, but preferably is substituted or unsubstituted C₆₀、C₇₀、C₈₆Fullerene, particularly preferably PCBM ([6, 6]]-phenyl-C61-butyric acid methyl ester, manufactured by Sigma-Aldrich Co.LLC, etc.) and analogs thereof (C₆₀Partial substitution with C₇₀、C₈₆A compound obtained by substituting a benzene ring of a substituent with another aromatic ring or heterocyclic ring, a compound obtained by substituting a methyl ester with n-butyl ester, isobutyl ester, or the like). The electron-deficient phthalocyanine group is phthalocyanine (F) in which 4 or more electron-withdrawing groups are bonded to each central metal₁₆MPc, and FPc-S8, wherein M represents a central metal, Pc represents phthalo cyan, S8 represents (n-octylsulfonyl)), naphthalocyanine, anthracyanine, substituted or unsubstituted tetrapyrazino-porphyrazines, and the like. The naphthalene tetracarbonyl compound may be any compound, but is preferably naphthalene tetracarboxylic dianhydride (NTCDA), naphthalene diimide compound (NTCDI), perinone Pigment (Pigment Orange)43, Pigment Red (Pigment Red)194, or the like). The perylene tetracarbonyl compound may be any compound, but is preferably perylene tetracarboxylic anhydride (PTCDA), perylene bisimide compound (PTCDI), or benzimidazole fused ring compound (PV). TCNQ compound means substituted or unsubstituted TCNQ, and a compound obtained by substituting the benzene ring portion of TCNQ with another aromatic ring or heterocyclic ring, and is exemplified by TCNQ, TCAQ (tetracyanoquinodimethane), TCN3T (2,2 '- ((2E, 2' E) -3 ', 4' -alkyl substituted-5H, 5 'H- [2, 2': 5 ', 2' -trithiophene)]-5,5 "-diimine) dipropionitrile derivative (2,2 ' - ((2E, 2 ' E) -3 ', 4 ' -Alkyl sulfonated-5H, 5 ' H- [2,2 ': 5 ', 2" -terthiophene)]-5,5 "-dimethyl idene) diamononitrile derivatives), and the like. Graphene may also be mentioned. Particularly preferred examples of the n-type organic semiconductor material are shown below.

R in the formula may be any group, but is preferably any of a hydrogen atom, a substituted or unsubstituted, branched or straight-chain alkyl group (preferably having 1 to 18 carbon atoms, more preferably having 1 to 12 carbon atoms, and still more preferably having 1 to 8 carbon atoms), and a substituted or unsubstituted aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, and still more preferably having 6 to 14 carbon atoms). Me is methyl.

[ chemical formula 2]

The number of organic materials contained in the organic semiconductor layer, which exhibit the characteristics of the semiconductor, may be 1, or 2 or more.

In general, the above materials are mixed in a solvent, applied in a layer form on a substrate, and dried to form a film. As an application method, reference can be made to the description of the water-soluble resin layer described later.

Examples of the solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, and 1-methylnaphthalene; 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, chlorotoluene, and the like; ester-based solvents such as ethyl acetate, butyl acetate, and amyl acetate; alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellulose solvent, ethyl cellulose solvent, and ethylene glycol; ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, and anisole; examples of the polar solvent include polar solvents such as N, N-dimethylformamide, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, and dimethylsulfoxide. These solvents may be used in only 1 kind, or 2 or more kinds.

The proportion of the organic semiconductor in the composition for forming an organic semiconductor layer (composition for forming an organic semiconductor) is preferably 0.1 to 80% by mass, more preferably 0.1 to 30% by mass, whereby a film having an arbitrary thickness can be formed.

Further, a resin binder may be blended in the composition for forming an organic semiconductor. In this case, the film-forming material and the binder resin can be dissolved or dispersed in the aforementioned appropriate solvent to prepare a coating liquid and form a thin film by various coating methods. Examples of the resin binder include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethacrylate, cellulose, polyethylene, and polypropylene, copolymers thereof, photoconductive polymers such as polyvinylcarbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene. The resin binder may be used alone, or a plurality of resin binders may be used in combination. In view of the mechanical strength of the film, a glass-transition temperature-high resin binder is preferable, and in view of the charge mobility, a resin binder containing a photoconductive polymer or a conductive polymer having a structure not containing a polar group is preferable.

In the case of blending the resin binder, the blending amount thereof is preferably 0.1 to 30 mass% in the organic semiconductor layer. The resin binder may be used in only 1 kind, or may be used in 2 or more kinds. In the case of using 2 or more species, the total amount is preferably within the above range.

Depending on the application, a mixed solution containing various semiconductor materials and additives can be applied to a substrate or the like to form a mixed film containing various material types. For example, in the case of manufacturing a photoelectric conversion layer, a mixed solution with another semiconductor material or the like can be used.

In addition, during film formation, the substrate may be heated or cooled, and the film quality or the deposition of molecules in the film may be controlled by changing the temperature of the substrate. The temperature of the substrate is not particularly limited, but is preferably-200 to 400 ℃, more preferably-100 to 300 ℃, and still more preferably 0to 200 ℃.

The formed organic semiconductor layer can be adjusted in characteristics by post-treatment. For example, the film morphology or the deposition of molecules in the film can be changed by exposing the solvent subjected to heat treatment or vapor deposition, thereby improving the properties. Further, by exposing the film to an oxidizing or reducing gas, a solvent, a substance, or the like, or mixing these, an oxidation or reduction reaction is caused, and the carrier density in the film can be adjusted.

The thickness of the organic semiconductor layer is not particularly limited, and varies depending on the kind of electronic device used, but is preferably 5nm to 50 μm, more preferably 10nm to 5 μm, and still more preferably 20nm to 500 nm.

< Water-soluble resin layer (Water-soluble resin composition) >

The water-soluble resin layer preferably contains a water-soluble resin and is formed of a water-soluble resin composition. The water-soluble resin is a resin having an amount of resin soluble in 100g of water at 20 ℃ of 1g or more, preferably 5g or more, more preferably 10g or more, and further preferably 30g or more. Although there is no upper limit, 20g is practical.

Specific examples of the water-soluble resin include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (water-soluble celluloses (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, and the like), pullulan or pullulan derivatives, starch, hydroxypropyl starch, carboxymethyl starch, chitosan, and cyclodextrin), polyethylene oxide, and polyethyloxazoline, with PVP and PVA being preferred, and PVA being more preferred. Further, 2 or more species different in main chain structure may be selected from among them and used, or may be used as a copolymer.

The weight average molecular weight of the water-soluble resin is not particularly limited, but the weight average molecular weight of the polyvinylpyrrolidone used in the present invention is preferably 50,000 to 400,000. The weight average molecular weight of the polyvinyl alcohol used in the present invention is preferably 15000 to 100,000. Among the other resins, the range of 10,000 to 300,000 is preferable.

The degree of dispersion (weight average molecular weight/number average molecular weight) of the water-soluble resin (PVP, PVA) used in the present invention is preferably 1.0 to 5.0, and more preferably 2.0 to 4.0.

The content of the water-soluble resin in the water-soluble resin composition may be appropriately adjusted as needed, but is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 4% by mass or more.

The thickness of the water-soluble resin layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1.0 μm or more, and still more preferably 2.0 μm or more. The upper limit of the thickness of the water-soluble resin layer is preferably 10 μm or less, more preferably 5.0 μm or less, and still more preferably 3.0 μm or less.

The water-soluble resin layer can be formed by applying a water-soluble resin composition containing 1 or 2 or more of the above water-soluble resins to the organic semiconductor layer and drying the composition. Generally, the water-soluble resin composition contains water as a solvent, and may further contain other additives.

The solid content concentration of the water-soluble resin composition is preferably 0.5 to 30% by mass, more preferably 1.0 to 20% by mass, and still more preferably 2.0 to 14% by mass. By setting the solid content concentration within the above range, uniform coating can be performed.

Coating is preferable as an application method. Examples of suitable methods include slit coating, casting, knife coating, wire bar coating, spray coating, dip (Dipping) coating, liquid bead coating, air knife coating, curtain coating, ink jet coating, spin coating, Langmuir-Blodgett (LB) method, and the like. More preferably, a casting method, a spin coating method, and an ink jet method are used. By this step, a water-soluble resin layer having a smooth surface and a large area can be produced at low cost.

The water-soluble resin composition preferably further contains a surfactant for improving coatability.

The surfactant may be any of nonionic, anionic, amphoteric fluorine-based, and the like as long as it lowers the surface tension. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan trioleate, sorbitan alkyl esters such as glycerol monostearate and monoglyceryl alkyl esters such as glycerol monooleate, and acetylene glycols such as fluorine-or silicon-containing oligomers and ethylene oxide adducts of acetylene glycols; anionic surfactants such as alkylbenzenesulfonate salts such as sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonate salts such as sodium butylnaphthalenesulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate and sodium octylnaphthalenesulfonate, alkylsulfonate salts such as sodium lauryl sulfate, alkylsulfonate salts such as sodium dodecylbenzenesulfonate, and sulfosuccinate salts such as sodium dilaurylsulfosuccinate; alkyl betaines such as lauryl betaine and stearyl betaine, and amphoteric surfactants such as amino acids.

When the water-soluble resin composition contains a surfactant, the amount of the surfactant added is preferably 0.001 to 20% by mass, more preferably 0.001 to 5% by mass, and still more preferably 0.01 to 1% by mass in the solid content. These surfactants may be used in only 1 kind, or may be used in 2 or more kinds. In the case of using 2 or more species, the total amount is preferably within the above range.

< photosensitive layer (photosensitive resin composition) >)

The photosensitive layer is formed from a composition for forming a photosensitive layer containing an acid generator and a resin. The weight average molecular weight of the acid-reactive resin in the photosensitive layer is 10,000 or more, preferably 15,000 or more, and more preferably 20,000 or more. The upper limit value is 50,000 or less, preferably 45,000 or less. In the present invention, there is value in that even when such a resin having a large molecular weight is used, a pattern can be appropriately formed.

The amount of the component having a weight average molecular weight of 1,000 or less contained in the acid-reactive resin is preferably 10% by mass or less, more preferably 5% by mass or less of the total acid-reactive resin components. With this configuration, the sensitivity fluctuation between resin production lots can be reduced.

The degree of dispersion (weight average molecular weight/number average molecular weight) of the acid-reactive resin is preferably 1.0 to 4.0, more preferably 1.1 to 2.5.

In the present invention, the weight molecular weight is a value measured by the method shown in examples.

The photosensitive resin composition forming the photosensitive layer may contain a solvent. An example of the method is one in which the amount of solvent contained in the photosensitive resin composition is 1 to 10% by mass. The photosensitive layer is preferably a chemically amplified photosensitive layer. The photosensitive layer is chemically amplified, whereby high storage stability and fine pattern formability can be achieved.

The content of the acid-reactive resin in the photosensitive layer is preferably 20 to 99.9 mass%, more preferably 40 to 99 mass%, and still more preferably 70 to 99 mass%. 1 or 2 or more acid-reactive resins may be contained. In the case of using 2 or more species, the total amount is preferably within the above range.

In the present invention, the acid-reactive resin may be a mixture of a resin having a high dissolution rate of butyl acetate and a resin having a low dissolution rate of butyl acetate. For example, a mixture of an acid-reactive resin having a dissolution rate of less than 20nm/s and a resin having a dissolution rate of more than 200nm/s is exemplified. The dissolution rate in this case is a dissolution rate of a composition in which the acid-reactive resin is replaced with the acid-reactive resin, measured by the method described in example 1 described later.

The photosensitive layer is preferably such that an exposed portion thereof is hardly soluble in a developer containing an organic solvent. The hardly soluble means that the exposed portion is hardly dissolved in a developer, specifically, 50mJ/cm at least at 1 of 365nm (i-ray), 248nm (KrF-ray) and 193nm (ArF-ray)²When the exposure is carried out at the above irradiation dose, the polarity changes, and it is preferable that the hardly soluble sp value (dissolution parameter value) is less than 19(MPa)^1/2More preferably, the solvent (B) is hardly soluble in 18.5(MPa)^1/2The following solvent is more preferably hardly soluble in 18.0(MPa)^1/2The following solvents. More preferably, the radiation passes at least 1 of 365nm (i-ray), 248nm (KrF-ray) and 193nm (ArF-ray) at 50-250 mJ/cm²The polarity of the exposure is changed as described above.

The photosensitive layer may be a negative photosensitive layer or a positive photosensitive layer, but is preferably a negative photosensitive layer because a finer groove or hole pattern can be formed.

From the viewpoint of improving the analytical ability, the thickness of the photosensitive layer is preferably 0.5 μm or more, and may exceed 1.0 μm, may be 1.5 μm or more, and may be 1.8 μm or more. The upper limit of the thickness of the photosensitive layer is preferably 10 μm or less, more preferably 5.0 μm or less, and may be 3.0 μm or less.

Further, the total thickness of the photosensitive layer and the water-soluble resin layer is preferably 2.0 μm or more. The upper limit is preferably 20.0 μm or less, more preferably 10.0 μm or less, and still more preferably 5.0 μm or less.

The photosensitive layer preferably has photosensitivity to irradiation of i-rays. The photosensitivity means a property that the material is modified by irradiation with at least one of an activating ray and a radiation ray (i-ray irradiation in the case of having photosensitivity to i-ray irradiation), and the modification of the material in the present invention is accompanied by a change in the dissolution rate of butyl acetate.

The over-development coefficient of the photosensitive layer is preferably 1.0 to 4.0, more preferably 1.1 to 1.9. By setting the thickness within such a range, effects such as suppression of pattern fitting and undercut can be effectively exhibited. The excessive development coefficient was measured and calculated according to the description of the examples described later.

The photosensitive resin composition is preferably a chemically amplified photosensitive resin composition containing at least an acid-reactive resin and a photoacid generator.

Dissolution speed

In the present invention, the dissolution rate when the non-irradiated photosensitive layer is immersed in butyl acetate at 23 ℃ is set to 20 nm/sec or more and 200 nm/sec or less. The dissolution rate is preferably 180 nm/sec or less, more preferably 150 nm/sec or less, and still more preferably 120 nm/sec or less. The lower limit is preferably 25 nm/sec or more, more preferably 40 nm/sec or more, and still more preferably 70 nm/sec or more. When the dissolution rate is within the above range, the occurrence of undercut of the photosensitive layer is suppressed or prevented, and the pattern collapse caused by the undercut is prevented in combination with the static contact angle of the photosensitive resin composition defined below, and the peeling of the photosensitive layer can be effectively suppressed. In the present specification, the method for measuring the dissolution rate of the photosensitive layer is based on the method employed in the examples described below.

Acid-reactive resin

The acid-reactive resin is a resin component constituting the photosensitive resin composition, and the dissolution rate of butyl acetate is changed by the action of an acid derived from a compound that generates an acid by irradiation with at least one of activating light and radiation. The acid-reactive resin used in the present invention is a hydrophobic resin soluble in butyl acetate at 23 ℃.

The acid-reactive resin is a resin component constituting the photosensitive resin composition, and is generally a resin containing a structural unit containing a group dissociated by an acid, and may contain another structural unit.

The acid-reactive resin is preferably soluble in an sp value (value of the dissolution parameter) of 18.0(MPa)^1/2An organic solvent which is hardly soluble in a solvent having an sp value of 18.0(MPa) when a tetrahydrofuran group in a structural unit represented by the following formula (1) is decomposed or dissociated^1/2The following organic solvent resins.

Here, the "sp-soluble value (value of dissolution parameter)" is 18.0(MPa)^1/2The organic solvent "means that a coating film (thickness: 1 μm) of a compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating the solution at 100 ℃ for 1 minute has a dissolution rate of butyl acetate of 20 nm/sec or more at 23 ℃ and a" hard-to-dissolve sp value of 18.0(MPa)^1/2The organic solvent "below means that the dissolution rate of a coating film (thickness of 1 μm) of a compound (resin) formed by applying a solution of the compound (resin) onto a substrate and heating the solution at 100 ℃ for 1 minute, with respect to butyl acetate at 23 ℃ is less than 0.1 nm/sec.

In the present invention, the acid-reactive resin preferably changes in dissolution rate by the action of an acid, and more preferably, the change is a decrease in dissolution rate. Acid-reactive tree before irradiation with activating light or the likeThe sp value of the fat was 18.0(MPa)^1/2The dissolution rate of the following organic solvent (typically, butyl acetate) is more preferably 40 nm/sec or more. When the acid-decomposable group of the acid-reactive resin is decomposed by irradiation with an activating light beam or the like, the sp value is 18.0(MPa)^1/2The dissolution rate of the following organic solvent (typically, butyl acetate) is more preferably less than 0.05 nm/sec.

The dissolution rate of the photosensitive layer or the acid-reactive resin may be changed according to a conventional method, but can be adjusted by, for example, selecting the molecular weight and molecular structure of a polymer constituting the acid-reactive resin, selecting the kind of the acid protecting group, introducing the acid and the protecting group into the molecule, selecting the kind of the acid generator, adjusting the ratio of the acid-reactive resin to the acid generator, the sp value of the resin, the ratio of the low-molecular compound in the solid content, and the like. Specifically, for the purpose of increasing the dissolution rate, there can be exemplified a method of decreasing the molecular weight of the resin, bringing the SP value of the resin close to the SP value of butyl acetate, and increasing the low molecular weight ratio in the solid content. On the other hand, in order to decrease the dissolution rate, there can be exemplified a method of increasing the molecular weight of the resin, separating the SP value of the resin from the SP value of butyl acetate, and decreasing the low molecular weight ratio in the solid content. Also, a resin having a dissolution rate of less than 20nm/s and a resin having a dissolution rate of more than 200nm/s may be mixed.

< protecting group >)

In the present invention, in the acid-reactive resin, 50 to 100 mol% of groups soluble in an aqueous alkali solution in all the structural units are protected by a hydrophobic protecting group. Here, the group soluble in an aqueous alkali solution is preferably a structural unit having an acid group. Examples of the acid group include a hydroxyl group (including a phenolic hydroxyl group), a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group, a phosphoric acid group, and a phosphonic acid group. The structural unit typically refers to a repeating structural unit of a polymer (may be simply referred to as a structural unit), but sometimes refers to a substituent or a generic term for several substituents in the structural unit. The protection by a hydrophobic protecting group is typically a state in which a functional group (usually an acid group) of a group soluble in the aqueous alkali solution is substituted with a hydrophobic substituent. For example, a mode in which a phenolic hydroxyl group is substituted with a substituent having an alkyl group to form an ether bond is exemplified. Alternatively, an ester may be formed by substituting a carboxyl group with a tetrahydropyranyl group. Protection based on the above hydrophobic protecting group can be evaluated by how many proportions the hydrophobic substituent is substituted with respect to the number of functional groups (usually acid groups) that the aqueous base-soluble group present in one molecule has.

When the ratio is expressed on a molar ratio basis, the ratio is 50 mol% or more and 100 mol% or less, preferably 55 mol% or more and 100 mol% or less, and more preferably 60 mol% or more and 100 mol% or less, as described above. The alkyl group to be a protective group may be a primary alkyl group, a secondary alkyl group, a tertiary alkyl group, a chain, a ring, a straight chain, or a branched chain. The alkyl group may be interrupted by an oxygen atom or a carbonyl group. Can be cyclic and form an oxazine ring or a tetrahydrofuran ring. And may be substituted with an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms). The ratio of 1 to 12 inserted oxygen atoms to 1 carbon atom is preferred. Alternatively, examples of the substituent A of the formula (2) described later may be mentioned.

Among them, the acid-reactive resin is preferably an acrylic polymer.

(acrylic acid-based Polymer)

The "acrylic polymer" is an addition polymerization type resin, is a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof, and may contain a structural unit other than a structural unit derived from (meth) acrylic acid or an ester thereof, for example, a structural unit derived from a styrene or a structural unit derived from a vinyl compound, or the like. In the acrylic polymer, the structural unit derived from (meth) acrylic acid or an ester thereof is preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably only the structural unit derived from (meth) acrylic acid or an ester thereof is contained, with respect to all the structural units in the polymer. Such acrylic polymers are preferably used for negative tone development.

The acrylic polymer also preferably has a structural unit containing a protected carboxyl group or a protected phenolic hydroxyl group. Examples of the monomer capable of forming a structural unit containing a protected carboxyl group include (meth) acrylic acid protected with an acid-dissociable group.

Preferred examples of the monomer having a phenolic hydroxyl group include hydroxystyrene such as p-hydroxystyrene and α -methyl-p-hydroxystyrene. Among them, α -methyl-p-hydroxystyrene is more preferable.

The acrylic polymer preferably has a cyclic ether ester structure, and more preferably has a structure represented by the following formula (1).

[ chemical formula 3]

In the formula, R⁸Represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), L¹Represents a carbonyl group or a phenylene group, R¹～R⁷Each independently represents a hydrogen atom or an alkyl group. R⁸Preferably a hydrogen atom or a methyl group, more preferably a methyl group.

L¹Represents a carbonyl group or a phenylene group, preferably a carbonyl group.

R¹～R⁷Each independently represents a hydrogen atom or an alkyl group. R¹～R⁷Alkyl in (1) and R⁸The meaning is the same, and the preferred mode is the same. And, preferably, R¹～R⁷1 or more of (A) are hydrogen atoms, more preferably R¹～R⁷All are hydrogen atoms.

As the structural unit (1), particularly preferred are (1-1) and (1-2).

[ chemical formula 4]

The radical polymerizable monomer used for forming the structural unit (1) may be a commercially available one, or a compound synthesized by a known method may be used. For example, the synthesis can be performed by reacting (meth) acrylic acid with a dihydrofuran compound in the presence of an acid catalyst. Alternatively, the compound may be formed by polymerizing a precursor monomer and then reacting a carboxyl group or a phenolic hydroxyl group with a dihydrofuran compound.

Examples of the structural unit containing a protected phenolic hydroxyl group include structural units represented by the following formula (2).

[ chemical formula 5]

A represents a group which is eliminated by the action of a hydrogen atom or an acid. The group to be eliminated by the action of an acid is preferably an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an alkoxyalkyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryloxyalkyl group (preferably 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, further preferably 7 to 20 carbon atoms in total), an alkoxycarbonyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), or an aryloxycarbonyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms). A may further have a substituent. R¹⁰Represents a substituent. R⁹R in the formula (1)⁸Groups having the same meaning. nx represents an integer of 0to 3.

The group dissociated by an acid is preferably a structural unit having a group dissociated by an acid in the compounds described in paragraphs 0039 to 0049 of Japanese patent application laid-open No. 2008-197480, and is preferably a compound described in paragraphs 0052 to 0056 of Japanese patent application laid-open No. 2012-159830 (Japanese patent No. 5191567), and these contents are incorporated in the present specification.

Although a specific example of the structural unit (2) is shown, the present invention should not be construed as being limited thereto.

[ chemical formula 6]

[ chemical formula 7]

In the acrylic polymer, the proportion of the structural unit (1) and the structural unit (2) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 10 to 60 mol%. The acrylic polymer may contain only 1 kind of the structural unit (1), or may contain 2 or more kinds. In the case of using 2 or more species, the total amount is preferably within the above range.

The acid-reactive resin may contain a structural unit having a crosslinkable group. For details of the crosslinkable group, reference can be made to the descriptions of paragraphs 0032 to 0046 of Japanese patent application laid-open No. 2011-209692, and these contents are incorporated in the present specification.

The acid-reactive resin is also preferably in an embodiment containing a structural unit having a crosslinkable group (structural unit (3)), but is preferably in a configuration substantially not containing the structural unit (3) having a crosslinkable group. With this configuration, the photosensitive layer can be removed more effectively after the pattern formation. Here, the term "substantially" means, for example, 3 mol% or less, preferably 1 mol% or less of all the structural units of the acid-reactive resin.

The acid-reactive resin may contain another structural unit (4)). Examples of the radical polymerizable monomer for forming the structural unit (4) include compounds described in paragraphs 0021 to 0024 of Japanese patent application laid-open No. 2004-264623. Preferable examples of the structural unit (4) include structural units derived from at least 1 member selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, and an N-substituted maleimide. Among them, a hydrophobic monomer such as benzyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yloxyethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, alicyclic structure-containing (meth) acrylate of 2-methylcyclohexyl (meth) acrylate, or styrene is preferable.

The structural unit (4) may be used in 1 type, or may be used in combination with 2 or more types. The content of the monomer unit forming the structural unit (4) when the structural unit (4) is contained in all the monomer units constituting the acrylic polymer is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and still more preferably 5 to 40 mol%. In the case of using 2 or more species, the total amount is preferably within the above range.

Various methods are known for synthesizing an acrylic polymer, but for example, the acrylic polymer can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer for forming at least the structural unit (1), the structural unit (2), and the like in an organic solvent using a radical polymerization initiator.

As the acid-reactive resin, a copolymer obtained by adding 2, 3-dihydrofuran to an acid anhydride group in a precursor copolymer obtained by copolymerizing unsaturated polycarboxylic acid anhydrides at a temperature of about room temperature (25 ℃) to 100 ℃ in the absence of an acid catalyst is also preferable.

Preferred examples of the acid-reactive resin include the following resins.

BzMA/THFMA/t-BuMA (molar ratio: 20-60: 35-65: 5-30)

BzMA/THFAA/t-BuMA (molar ratio: 20-60: 35-65: 5-30)

BzMA/THPMA/t-BuMA (molar ratio: 20-60: 35-65: 5-30)

BzMA/PEES/t-BuMA (molar ratio: 20-60: 35-65: 5-30)

BzMA is benzyl methacrylate, THFMA is tetrahydrofuran-2-yl methacrylate, BuMA is butyl methacrylate, THFAA is tetrahydrofuran-2-yl acrylate, THPMA is tetrahydro-2H-pyran-2-yl methacrylate, PEES is p-ethoxyethoxystyrene.

Examples of the acid-reactive resin used for positive development include those described in jp 2013-011678 a, and these contents are incorporated in the present specification.

The content of the acid-reactive resin in the photosensitive resin composition is preferably 20 to 99% by mass, more preferably 40 to 99% by mass, and still more preferably 70 to 99% by mass, based on the total solid content of the photosensitive resin composition. When the content is within this range, pattern formability during development becomes good. The acid-reactive resin may contain only 1 species, or may contain 2 or more species. In the case of using 2 or more species, the total amount is preferably within the above range.

The acid-reactive resin preferably accounts for 10 mass% or more, more preferably 50 mass% or more, and still more preferably 90 mass% or more of the resin components contained in the photosensitive resin composition.

Photoacid generators

The photosensitive resin composition may include a photoacid generator. The photoacid generator is preferably a photoacid generator having absorption at a wavelength of 365 nm.

The photoacid generator is preferably a compound having an oxime sulfonate group (hereinafter, also simply referred to as oxime sulfonate compound).

The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105) described later.

[ chemical formula 8]

X³Represents an alkyl group, an alkoxy group or a halogen atom. In the presence of a plurality of X³In this case, they may be the same or different. X is above³The alkyl group and the alkoxy group in (1) may have a substituent. As the above X³The alkyl group in (1) is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. As the above X³The alkoxy group in (3) is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. As the above X³The halogen atom in (1) is preferably a chlorine atom or a fluorine atomAnd (4) adding the active ingredients.

m3 represents an integer of 0to 3, preferably 0 or 1. When m3 is 2 or 3, plural X' s³May be the same or different.

R³⁴Represents an alkyl group or an aryl group, and is preferably 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, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W, or an anthracenyl group which may be substituted by 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, a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

Wherein m3 is 3, X³Is methyl, X³In the ortho position, R³⁴Particularly preferred are compounds having a linear alkyl group having 1 to 10 carbon atoms, a 7, 7-dimethyl-2-oxonorbornanemethyl group and a p-toluyl group.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include the following compounds described in Japanese patent application laid-open Nos. 0064 to 0068 of 2011-209692, and the contents of these are incorporated in the present specification.

[ chemical formula 9]

R¹¹Represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R may be present¹²Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and there may be a plurality of R¹⁶Independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, ns represents 1 or 2, and ms represents an integer of 0to 6.

From R¹¹The alkyl group, aryl group or heteroaryl group represented may have a substituent. As a group consisting of R¹¹The alkyl group is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent. As a group consisting of R¹¹To representExamples of the substituent which may be contained in the alkyl group of (a) include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group. As a group consisting of R¹¹Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, and benzyl.

And, as represented by R¹¹The aryl group is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent. As a group consisting of R¹¹Examples of the substituent which the aryl group may have include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group and an alkoxysulfonyl group. As a group consisting of R¹¹The aryl group represented by (a) is preferably a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group. And, as represented by R¹¹The heteroaryl group is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent. As a group consisting of R¹¹Examples of the substituent which the heteroaryl group may have include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group and an alkoxysulfonyl group. From R¹¹The heteroaryl group represented may have at least 1 heteroaromatic ring, for example, the heteroaromatic ring may also be fused with a benzene ring. As a group consisting of R¹¹Examples of the heteroaryl group include those obtained by removing 1 hydrogen atom from a ring selected from the group consisting of 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.

R¹²Preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Sometimes there are more than 2R in the compound¹²Of which preferably 1 or 2 are alkyl, aryl or halogen atoms, more preferably 1 is an alkyl, aryl or halogen atom,it is particularly preferred that 1 is an alkyl group and the remainder is a hydrogen atom.

From R¹²The alkyl group or the aryl group represented may have a substituent.

As a group consisting of R¹²Examples of the substituent which the alkyl group or the aryl group may have include the above-mentioned W.

As a group consisting of R¹²The alkyl group is preferably an alkyl group having 1 to 12 total carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 6 total carbon atoms which may have a substituent.

As a group consisting of R¹²The alkyl group represented by (i) is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a n-hexyl group, an allyl group, a chloromethyl group, a bromomethyl group, a methoxymethyl group, or a benzyl group, more preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, or a n-hexyl group, still more preferably a methyl group, an ethyl group.

As a group consisting of R¹²The aryl group is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

As a group consisting of R¹²The aryl group represented by (A) 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.

As a group consisting of R¹²Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, chlorine atom and bromine atom are preferable.

X represents O or S, preferably O. In the above formulas (OS-103) to (OS-105), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.

ns represents 1 or 2, ns is preferably 1 in the case where X is O, and ns is preferably 2 in the case where X is S.

From R¹⁶The alkyl group and the alkoxy group may have a substituent.

As a group consisting of R¹⁶The alkyl group is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

As a group consisting of R¹⁶The alkyl group represented mayExamples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

As a group consisting of R¹⁶The alkyl group is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, a n-decyl group, a n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, or a benzyl group.

As a group consisting of R¹⁶The alkoxy group is preferably an alkoxy group having 1 to 30 total carbon atoms which may have a substituent.

As a group consisting of R¹⁶Examples of the substituent which the alkoxy group may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

As a group consisting of R¹⁶The alkoxy group represented is preferably a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, a phenoxyethoxy group, a trichloromethoxy group or an ethoxyethoxy group.

As R¹⁶Examples of the aminosulfonyl group in (1) include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group and an aminosulfonyl group.

As a group consisting of R¹⁶Examples of the alkoxysulfonyl group include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group and a butoxysulfonyl group.

ms represents an integer of 0to 6, preferably an integer of 0to 2, more preferably 0 or 1, and particularly preferably 0.

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 the above formula (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 particularly preferably a compound represented by the following formula (OS-108) or (OS-109).

[ chemical formula 10]

R¹¹Represents alkyl, aryl or heteroaryl, R¹⁷Represents a hydrogen atom or a bromine atom, R¹⁸Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group, R¹⁹Represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R²⁰Represents a hydrogen atom or a methyl group.

R¹⁷Represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

R¹⁸Represents 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 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, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

R¹⁹Represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R²⁰Represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

In the oxime sulfonate compound, the oxime may have either one or a mixture of the three-dimensional structures (E, Z).

Specific examples of oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include compounds described in paragraphs 0088 to 0095 of Japanese patent application laid-open No. 2011-209692, and the contents thereof are incorporated herein.

As another preferred embodiment of the oxime sulfonate compound having at least 1 oxime sulfonate group, there can be mentioned compounds represented by the following formulae (OS-101) and (OS-102).

[ chemical formula 11]

R¹¹Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl groupAcyl, carbamoyl, sulfamoyl, sulfo, cyano, aryl or heteroaryl. R¹¹More preferably a cyano or aryl radical, R¹¹More preferably, a cyano group, a phenyl group or a naphthyl group.

R^12aRepresents an alkyl group or an aryl group.

X represents-O-, -S-, -NH-, -NR¹⁵-、-CH₂-、-CR¹⁶H-or-CR¹⁶R¹⁷-，R¹⁵～R¹⁷Each independently represents an alkyl group or an aryl group.

R²¹～R²⁴Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amido group, a sulfo group, a cyano group or an aryl group. R²¹～R ²⁴2 of them may be bonded to each other to form a ring. At this time, the rings may be condensed to form a condensed ring together with the benzene ring.

As R²¹～R²⁴Preferably a hydrogen atom, a halogen atom or an alkyl group, and, also preferably R²¹～R²⁴At least 2 of them are bonded to each other to form an aryl group. Among them, R is preferred²¹～R²⁴All by way of hydrogen atoms.

The above-mentioned substituents may each have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).

In the oxime sulfonate compound, the oxime or benzothiazole ring may have any one or a mixture of the three-dimensional structures (E, Z, etc.).

Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of Japanese patent application laid-open No. 2011-209692, and the contents thereof are incorporated in the present specification.

Among the above compounds, b-9, b-16, b-31 and b-33 are preferable.

Examples of commercially available products include WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Kagaku Co., Ltd.), and the like.

The photoacid generator which is sensitive to activating light preferably does not contain 1, 2-quinonediazide. The reason is that: although the carboxyl group is generated by the step-wise photochemical reaction, the 1, 2-quinonediazide has a quantum yield of 1 or less and is less sensitive than the oxime sulfonate compound.

On the other hand, since the oxime sulfonate compound acts as a catalyst for deprotection of an acid-protected acid group generated by induction of activation light, an acid generated by the action of 1 photon contributes to a plurality of deprotection reactions, and the quantum yield exceeds 1, for example, a value as large as a number square of 10, and it is presumed that high sensitivity can be obtained as a result of so-called chemical amplification.

Further, since the oxime sulfonate compound contains a pi-conjugated system having a wide range, it has absorption up to a long wavelength side, and exhibits very high sensitivity not only to Deep Ultraviolet (DUV), ArF radiation, KrF radiation, i-radiation, but also to g-radiation.

By using a tetrahydrofuranyl group as the acid decomposable group in the acid-reactive resin, acid decomposability equivalent to or higher than that of an acetal or ketal can be obtained. This enables the acid decomposable groups to be reliably consumed by the post-baking for a shorter period of time. Further, by using an oxime sulfonate compound as a photoacid generator in combination, the generation rate of sulfonic acid is increased, so that the generation of acid is promoted, and the decomposition of the acid decomposable group of the resin is promoted. Further, since the acid obtained by decomposition of the oxime sulfonate compound is a sulfonic acid having a small molecule, the diffusibility in the cured film is also high, and further high sensitivity can be achieved.

The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, based on the total solid content of the photosensitive resin composition.

The photoacid generator may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In the case of using 2 or more species, the total amount is preferably within the above range.

Other components

The photosensitive resin composition may contain other components.

The other component preferably contains an organic solvent from the viewpoint of coatability.

Organic solvent

The photosensitive resin composition preferably contains an organic solvent, and in addition to the reactive resin, any of the photoacid generator and various additives is preferably prepared as a solution dissolved in the organic solvent.

As the organic solvent used in the photosensitive resin composition, known organic solvents can be used, and examples thereof include 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 acetates, esters, ketones, amides, lactones, and the like.

Examples of the organic solvent 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; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate; (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; (5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether; (6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; (7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; (8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate; (9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether; (10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether; (11) dipropylene glycol monoalkylether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate; (12) lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-pentyl lactate, and isoamyl lactate; (13) aliphatic carboxylic acid esters such as n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, and isobutyl butyrate; (14) other esters such as ethyl glycolate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate; (15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; (16) amides such as N-methylformamide, N-dimethylformamide, N-methylacetamide, N-dimethylacetamide, and N-methylpyrrolidone; (17) lactones such as γ -butyrolactone.

Further, if necessary, an organic solvent such as benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate, or the like may be added to these organic solvents.

Among the above organic solvents, 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 organic solvents can be used alone in 1 kind, or can be mixed with 2 or more kinds.

In the case of using 2 or more species, the total amount is preferably within the above range.

Further, the photosensitive resin composition preferably contains a basic compound from the viewpoint of liquid storage stability, and preferably contains a surfactant from the viewpoint of coatability.

Basic compound

The photosensitive resin composition preferably contains a basic compound.

The basic compound can be arbitrarily selected from compounds used for chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.

Examples of the aromatic amine include aniline, benzylamine, N-dimethylaniline, and diphenylamine.

Examples of the heterocyclic amine 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 and nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexylmorpholinylethylthiourea, piperazine, morpholine, 4-methylmorpholine, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo [5.3.0] -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 a carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, and the like.

When the photosensitive resin composition contains a basic compound, the content of the basic compound is preferably 0.001 to 1 part by mass, more preferably 0.002 to 0.5 part by mass, per 100 parts by mass of the acid-reactive resin.

The basic compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds, but preferably used in combination in 2 or more kinds, more preferably used in combination in 2 kinds, and further preferably used in combination in 2 kinds of heterocyclic amines. In the case of using 2 or more species, the total amount is preferably within the above range.

Surface active agent

The photosensitive resin composition preferably contains a surfactant.

As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferable surfactant is a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based surfactants, and silicon-based surfactants.

The surfactant is more preferably a fluorine-based surfactant, a silicon-based surfactant, or a combination thereof.

Examples of such fluorine-based surfactants and silicon-based surfactants include those described in Japanese patent application laid-open Nos. 62-036663, 61-226746, 61-226745, 62-170950, 63-034540, 7-230165, 8-062834, 9-054432, 9-005988 and 2001-330953, and commercially available surfactants can also be used.

Examples of commercially available surfactants that can be used include fluorine-based surfactants and silicon-based surfactants such as Eftop EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Fluorad FC430 and 431 (manufactured by Sumitomo 3M Limited), Megaface F171, F173, F176, F189, and R08 (manufactured by DIC CORPORATION), Surflon S-382, SC101, 102, 103, 104, 105, and 106 (manufactured by Sumitomo S. ASAHI GLASS CO., LTD.), and PolyFox series (manufactured by OMNOVA SOLUTION INC., PF-6320). Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicone surfactant.

Further, as a preferable example, there can be mentioned a copolymer containing a structural unit a and a structural unit B represented by the following formula (41) and having a weight average molecular weight (Mw) as measured by gel permeation chromatography in terms of polystyrene when Tetrahydrofuran (THF) is used as a solvent, of 1,000 or more and 10,000 or less.

[ chemical formula 12]

(in the formula, R⁴¹And R⁴³Each independently represents a hydrogen atom or a methyl group, R⁴²Represents a linear alkylene group having 1 to 4 carbon atoms, R⁴⁴Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L⁴Represents an alkylene group having 3 to 6 carbon atoms, p4 and q4 are mass percentages representing a polymerization ratio, p4 represents a numerical value of 10 to 80 mass%, q4 represents a numerical value of 20 to 90 mass%, r4 represents an integer of 1 to 18, and n4 represents an integer of 1 to 10. )

L above⁴A branched alkylene group represented by the following formula (42) is preferable. R in the formula (42)⁴⁵Represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 2 or 3 carbon atoms, from the viewpoint of wettability to the surface to be coated.

-CH₂-CH(R⁴⁵)- (42)

The weight average molecular weight of the copolymer is more preferably 1,500 or more and 5,000 or less.

When the surfactant is contained, the amount of the surfactant added is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass, and still more preferably 0.01 to 1 part by mass, per 100 parts by mass of the acid-reactive resin.

The surfactant can be used alone in 1 kind, or can be mixed with 2 or more kinds. In the case of using 2 or more species, the total amount is preferably within the above range.

Water content

The photosensitive resin composition may contain moisture. Preferably, the water content is low or no, but it is possible to include unavoidable moisture. The moisture content of the photosensitive resin composition is preferably 1 mass% or less, more preferably 0.7 mass% or less, and further preferably 0.4 mass% or less. The lower limit is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.05% by mass or more.

Metal impurity

In general, a minute amount of metal impurities is inevitably contained in the photosensitive resin composition. For example, salts of alkali metals or alkaline earth metals such as sodium, potassium and calcium may be mentioned. In the present invention, the total content of sodium ions, potassium ions, and calcium ions in the photosensitive resin composition is defined as, for example, in the range of 1 mass ppt to 1000 mass ppb, and further in the range of 50 mass ppt to 900 mass ppb.

The amount of metal ions was measured by the method described in the examples described below.

Other

Further, if necessary, 1 or 2 or more kinds of known additives such as an antioxidant, a plasticizer, a thermal radical generator, a thermal acid generator, an acid amplifier, an ultraviolet absorber, a thickener, an organic or inorganic precipitation inhibitor, and the like may be added. The details of these can be referred to the descriptions of paragraphs 0143 to 0148 of Japanese patent application laid-open No. 2011-209692, and these contents are incorporated in the present specification.

Static contact angle

In the present invention, the static contact angle of the photosensitive resin composition on the water-soluble resin layer is defined to be 60 ° or less. The static contact angle is preferably 50 ° or less, more preferably 40 ° or less, and further preferably 30 ° or less. The lower limit may be 0 °, but is preferably 2 ° or more, more preferably 5 ° or more, and further preferably 10 ° or more. The lower limit or higher more effectively realizes the in-plane uniformity of the film thickness during spin coating, and the upper limit or lower suppresses the foaming during coating.

In the present specification, the method for measuring the static contact angle of the photosensitive resin composition is based on the method used in the examples described below.

The static contact angle of the photosensitive resin composition can be changed according to a conventional method, but can be adjusted by, for example, adjusting the molecular weight, molecular structure, kind or amount of polar group of the polymer constituting the acid-reactive resin, kind or amount of the surfactant to be blended, and the like.

< kit >

The photosensitive resin composition may be a kit for forming a photosensitive layer and a water-soluble resin layer in this order in combination with a water-soluble resin composition containing a water-soluble resin. Further, it is preferably used as a kit for processing an organic semiconductor layer. In this case, as a specific embodiment, each component of the photosensitive resin composition and each component of the water-soluble resin composition are preferably applied. In the present invention, a kit obtained by combining the organic semiconductor-forming composition may be used. As a specific embodiment of the composition, the above-mentioned components of the organic semiconductor and the composition thereof are preferably applied.

< method for forming pattern of organic semiconductor layer >

The following embodiments can be mentioned as examples of a pattern forming method that can be preferably employed in the present invention. Processing (patterning) of the organic semiconductor layer is shown below as an example, but can also be used for patterning of layers other than the organic semiconductor layer.

The method for forming a pattern of an organic semiconductor layer according to this embodiment includes:

(1) a step of forming a water-soluble resin layer on the organic semiconductor layer;

(2) a step of forming a photosensitive layer on the side of the water-soluble resin layer opposite to the organic semiconductor layer;

(3) exposing the photosensitive layer;

(4) a step of developing the substrate with a developer containing an organic solvent to produce a mask pattern;

(5) removing at least the water-soluble resin layer and the organic semiconductor layer in the non-mask portion by dry etching; and

(6) and removing the water-soluble resin layer.

< (1) Process for producing a Water-soluble resin layer on an organic semiconductor layer

The method for forming a pattern of an organic semiconductor layer according to the present embodiment includes a step of forming a water-soluble resin layer on the organic semiconductor layer. Generally, this step is performed after an organic semiconductor layer is formed on a substrate. In this case, the water-soluble resin layer is formed on the surface of the organic semiconductor opposite to the surface on the substrate side. The water-soluble resin layer is usually provided on the surface of the organic semiconductor layer, but another layer may be provided within a range not departing from the gist of the present invention. Specifically, a water-soluble primer layer and the like can be given. The water-soluble resin layer may be provided with only 1 layer, or may be provided with 2 or more layers. As described above, the water-soluble resin layer is preferably formed using a water-soluble resin composition.

< (2) Process for Forming photosensitive layer on side of Water-soluble resin layer opposite to organic semiconductor layer

After the step (1), a photosensitive layer is formed using the photosensitive resin composition on the side of the water-soluble resin layer opposite to the organic semiconductor layer side (2). As described above, the photosensitive layer is preferably formed using a photosensitive resin composition, and more preferably a chemically amplified photosensitive resin composition containing an acid-reactive resin and a photoacid generator.

The chemically amplified photosensitive resin composition contains a photoacid generator, and when exposed to light, generates an acid, which reacts with an acid-reactive resin contained in the resist to form a pattern and function as a photosensitive layer.

The solid content concentration of the photosensitive resin composition is usually 1.0 to 40% by mass, preferably 10 to 35% by mass, and more preferably 16 to 28% by mass. By setting the solid content concentration within the above range, the photosensitive resin composition can be uniformly applied to the water-soluble resin layer, and a resist pattern having a high resolution and a rectangular outline (fidelity) can be formed. The solid content concentration refers to the percentage of the mass of the resist components other than the organic solvent with respect to the total mass of the photosensitive resin composition.

< 3 > Process for exposing photosensitive layer

After the photosensitive layer is formed in the step (2), the photosensitive layer is exposed. Specifically, the photosensitive layer is irradiated with an activating light beam through a mask having a predetermined pattern. The exposure may be performed only 1 time or may be performed a plurality of times.

Specifically, a substrate provided with a dried coating film of the photosensitive resin composition is irradiated with an activating ray in a predetermined pattern. The exposure may be performed through a mask, or a predetermined pattern may be directly drawn. As the activating light, activating light having a wavelength of preferably 180nm or more and 450nm or less, more preferably 365nm (i-ray), 248nm (KrF-ray) or 193nm (ArF-ray) can be used. After this step, a heating step (PEB) may be performed after the exposure, if necessary.

In the exposure by the activating light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generating device, a Light Emitting Diode (LED) light source, or the like can be used.

In the case of using a mercury lamp, it is possible to preferably use activating light having a wavelength of g-ray (436nm), i-ray (365nm), h-ray (405nm), or the like. In the present invention, it is preferable to use i-rays because the effects thereof can be exhibited appropriately.

In the case of using a laser, a solid-state (YAG) laser can be preferably used at 343nm or 355nm, an excimer laser can be preferably used at 193nm (ArF ray), 248nm (KrF ray), or 351nm (Xe ray), and a semiconductor laser can be preferably used at 375nm or 405 nm. Among them, 355nm and 405nm are more preferable from the viewpoint of stability, cost, and the like. The photosensitive layer can be irradiated with the laser light 1 time or a plurality of times.

The exposure is preferably 40 to 120mJ, more preferably 60 to 100 mJ.

The energy density per 1 pulse of the laser is preferably 0.1mJ/cm²Above and 10,000mJ/cm²The following. More preferably 0.3mJ/cm for sufficiently hardening the coating film²Above, more preferably 0.5mJ/cm²The above. More preferably 1,000mJ/cm so as not to decompose the coating film by ablation (ablation)²Hereinafter, more preferably 100mJ/cm²The following.

The pulse width is preferably 0.1 nanoseconds (hereinafter, referred to as "nsec") or more and 30,000nsec or less. In order not to decompose the color coating film by the ablation phenomenon, it is more preferably 0.5nsec or more, and still more preferably 1nsec or more. In order to improve the accuracy in accordance with the scanning exposure, the accuracy is more preferably 1,000nsec or less, and still more preferably 50nsec or less.

The frequency of the laser light is preferably 1Hz to 50,000Hz, and more preferably 10Hz to 1,000 Hz.

Further, the frequency of the laser beam is more preferably 10Hz or more, and still more preferably 100Hz or more in order to shorten the exposure processing time, and is more preferably 10,000Hz or less, and still more preferably 1,000Hz or less in order to improve the accuracy in the scanning exposure.

The laser is preferable to the mercury lamp in that the intersections are easily gathered, a mask for pattern formation in the exposure step is not required, and cost can be reduced.

The exposure apparatus is not particularly limited, but commercially available products such as Callisto (V-Technology co., ltd.), AEGIS (V-Technology co., ltd.), DF2200G (dainippon screen mfg.co., ltd.) and the like can be used. Also, devices other than those described above may also be preferably used.

Further, the irradiation light amount can be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter, as necessary.

< (4) Process for producing mask Pattern by developing with developer containing organic solvent

After exposure through the photosensitive layer in the step (3), development is performed using a developer containing an organic solvent (hereinafter, sometimes referred to as an organic developer). The development is preferably negative. The sp value of the solvent contained in the developer is preferably less than 19MPa^1/2More preferably 18MPa^1/2The following.

As the organic solvent contained in the developer, a polar solvent such as a copper-based solvent, an ester-based solvent, or an amide-based solvent, or a hydrocarbon-based solvent can be used.

Examples of the copper-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone (ionone), diacetone alcohol, acetyl alcohol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate.

Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl 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, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, and the like.

Examples of the amide solvent include N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, hexamethylphosphoric triamide, and 1, 3-dimethyl-2-imidazolidinone.

Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, and decane.

The organic solvent may be used alone in 1 kind, or may be used in combination with 2 or more kinds. Further, it may be used in combination with an organic solvent other than the above. However, the water content of the entire developer is preferably 10% by mass, and more preferably substantially no water. Here, the term "substantially" means that the water content of the entire developer is, for example, 3 mass% or less, and more preferably, measurement limit or less.

That is, the amount of the organic solvent used in the organic developer is preferably 90 mass% or more and 100 mass% or less, and more preferably 95 mass% or more and 100 mass% or less, with respect to the total amount of the developer.

In particular, the organic developer preferably contains at least 1 organic solvent selected from the group consisting of copper solvents, ester solvents, and amide solvents.

The organic developer may contain an appropriate amount of an alkali compound as needed. Examples of the basic compound include the compounds described in the above section of the basic compound.

The vapor pressure of the organic developer is preferably 5kPa or less, more preferably 3kPa or less, and further preferably 2kPa or less under the condition of 20 ℃. By setting the vapor pressure of the organic developer to 5kPa or less, evaporation of the developer on the substrate or in the developing cup can be suppressed, temperature uniformity in the wafer plane can be improved, and as a result, dimensional uniformity in the wafer plane can be improved.

Specific examples of the solvent having a vapor pressure of 5kPa or less include ester solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl isobutyl ketone, ester solvents such as butyl acetate, amyl acetate, isoamyl 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, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate, ester solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, amide solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as octane and decane.

Specific examples of the solvent having a vapor pressure of 2kPa or less in a particularly preferable range include copper-based solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenyl acetone, ester-based solvents such as 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-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, and propyl lactate, ester-based solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, and mixtures thereof, Amide solvents such as N, N-dimethylformamide, aromatic hydrocarbon solvents such as xylene, and aliphatic hydrocarbon solvents such as octane and decane.

An appropriate amount of 1 or 2 or more surfactants can be added to the developer as needed.

The surfactant is not particularly limited, and for example, the surfactants described in the above section of the water-soluble resin composition can be preferably used.

When the surfactant is blended in the developer, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.

As the developing method, for example, the following methods can be applied: a method of immersing the substrate for a certain period of time in a tank filled with a developing solution (immersion method), a method of developing by stacking a developing solution on the surface of the substrate by surface tension and standing for a certain period of time (liquid coating method), a method of spraying a developing solution on the surface of the substrate (spray method), a method of continuously spraying a developing solution on the substrate rotating at a constant speed while scanning a developing solution spraying nozzle at a constant speed (dynamic dispensing method), and the like.

In the case where the above-described various developing methods include a step of ejecting the developing solution from the developing nozzle of the developing device toward the photosensitive layer, the ejection pressure of the ejected developing solution (flow rate of the ejected developing solution per unit area) is preferably 2 mL/sec/mm²Hereinafter, more preferably 1.5 mL/sec/mm²Hereinafter, more preferably 1 mL/sec/mm²The following. The flow rate is not particularly limited, but is preferably 0.2 mL/sec/mm in consideration of the throughput²The above. By setting the ejection pressure of the ejected developer within the above range, pattern defects caused by the resist residue after development can be significantly reduced.

Although the details of this mechanism are not clear, it is presumably because: by setting the ejection pressure within the above range, the pressure of the developer applied to the photosensitive layer is reduced, and the resist pattern on the photosensitive layer can be suppressed from being unintentionally erased or destroyed.

Further, the ejection pressure of the developer (mL/sec/mm)²) Is the value in the outlet of the developing nozzle in the developing device.

Examples of the method of adjusting the ejection pressure of the developer include a method of adjusting the ejection pressure by a pump or the like, and a method of adjusting the pressure by supply from a pressure tank to change the ejection pressure.

After the step of performing development using a developer containing an organic solvent, the step of stopping the development while replacing the developer with another organic solvent may be performed.

< (5) A step of removing at least the water-soluble resin layer and the organic semiconductor layer in the non-mask portion by dry etching

After the photosensitive layer is developed to form a mask pattern, at least the water-soluble resin layer and the organic semiconductor layer in the non-mask portion are removed by etching. The non-mask portion indicates a portion where the photosensitive layer is removed in the developing step.

Specifically, in the dry etching, at least the water-soluble resin layer and the organic semiconductor layer are dry-etched using the resist pattern as an etching mask. Typical examples of dry etching include the methods described in Japanese patent application laid-open Nos. 59-126506, 59-046628, 58-009108, 58-002809, 57-148706 and 61-041102.

The dry etching is preferably performed in the following manner from the viewpoint of forming the pattern to have a more rectangular cross section and further reducing damage to the organic semiconductor layer.

The etching method preferably includes the following etching steps: the etching in stage 1 is carried out using a fluorine-based gas and oxygen (O)₂) Etching to the unexposed region (depth) of the organic semiconductor layer; etching in stage 2, and nitrogen (N) gas is used after the etching in stage 1₂) And oxygen (O)₂) The mixed gas of (2), preferably etched to the vicinity of the exposed region (depth) of the organic semiconductor layer; and overetching after the organic semiconductor layer is exposed. Hereinafter, a specific method of dry etching, as well as etching at stage 1, etching at stage 2, and overetching will be described.

The dry etching was performed by obtaining etching conditions in advance by the following method.

(1) The etching rate (nm/min) in the etching at the 1 st stage and the etching rate (nm/min) in the etching at the 2 nd stage were calculated, respectively. (2) The time required for etching the desired thickness by the etching of the 1 st stage and the time required for etching the desired thickness by the etching of the 2 nd stage are calculated. (3) The etching in stage 1 is performed based on the etching time calculated in (2) above. (4) The etching in the 2 nd stage is performed based on the etching time calculated in the above (2). Or the etching time may be determined by end point detection and the etching of stage 2 may be performed according to the determined etching time. (5) The overetching time was calculated for the total time of the above (3) and (4), and overetching was performed.

From the viewpoint of processing the organic material of the film to be etched into a rectangular shape, the mixed gas used in the etching step of the above-mentioned stage 1 preferably contains a fluorine-based gas and oxygen (O)₂). In the etching step of stage 1, the organic semiconductor layer is etched to a region not exposed to the outside, whereby damage to the organic semiconductor layer can be avoided. In the etching step of the 2 nd stage and the overetching step, it is preferable that etching is performed to a region where the organic semiconductor layer is not exposed by a mixed gas of a fluorine-based gas and an oxygen gas in the etching step of the 1 st stage, and then etching is performed using a mixed gas of a nitrogen gas and an oxygen gas in order to avoid damage to the organic semiconductor layer.

It is important to determine the ratio of the etching amount in the etching step at the 1 st stage to the etching amount in the etching step at the 2 nd stage so as not to impair the rectangularity of the etching treatment in the etching step at the 1 st stage. The latter ratio of the total etching amount (the sum of the etching amount in the etching step at the 1 st stage and the etching amount in the etching step at the 2 nd stage) is preferably in the range of more than 0% and 50% or less, and more preferably 10 to 20%. The etching amount is an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.

Also, the etching preferably includes an over-etching treatment. The overetching treatment is preferably performed by setting an overetching ratio. The over-etching ratio is preferably calculated from the first etching treatment time. The over-etching ratio can be arbitrarily set, but from the viewpoint of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched, the etching treatment time in the etching step is preferably 30% or less, more preferably 5 to 25%, and particularly preferably 10 to 15%.

< (6) Process for removing Water-soluble resin layer

After etching, the water-soluble resin layer is preferably removed using a solvent (usually water).

As a method for removing the water-soluble resin layer using water, for example, a method of removing the water-soluble resin layer by spraying washing water from a spray type or shower type spray nozzle to the resist pattern can be cited. As the cleaning water, pure water can be preferably used. Examples of the spray nozzle include a spray nozzle that includes the entire substrate within its spray range, and a spray nozzle that is a movable spray nozzle and includes the entire substrate within its movable range.

In the case where the spray nozzle is movable, the resist pattern can be removed more effectively by moving the spray nozzle 2 or more times from the center of the substrate to the end of the substrate in the step of removing the water-soluble resin layer and spraying the cleaning water.

After removing the water, a step such as drying is also preferably performed. The drying temperature is preferably 80 to 120 ℃.

< use >)

The photosensitive layer of the present invention can be used for the production of electronic devices using an organic semiconductor. Here, the electronic device includes a semiconductor, has 2 or more electrodes, and controls a current flowing between the electrodes or a voltage generated by the current, light, magnetism, a chemical substance, or the like, or generates light, an electric field, a magnetic field, or the like by an applied voltage or a current. Examples thereof 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 also be used for any of a photosensor application and an energy conversion application (solar cell). Among them, the use is preferably an organic field effect transistor, an organic photoelectric conversion element, or an organic electroluminescent element, more preferably an organic field effect transistor or an organic photoelectric conversion element, and particularly preferably an organic field effect transistor.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, "%" and "part" are based on mass.

< method for measuring weight average molecular weight (Mw) >

The Mw of the resin was measured by the following method.

< method for measuring weight average molecular weight (Mw) >

The molecular weight of the water-soluble resin is measured by the method described in paragraphs 0067 to 0071 of the WO 2015/098978.

The molecular weight of the other resins was measured by gel permeation chromatography (GPC measurement) under the following measurement conditions.

Polystyrene conversion value

The device comprises the following steps: HLC-8220 (manufactured by TOSOH CORPORATION)

Pipe column: protective tubing HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION)

Eluent: THF (tetrahydrofuran)

A detector: UV ray (ultraviolet ray) wavelength of 254nm

Examples 1 to 11 and comparative examples 1 to 3

< preparation of Water-soluble resin composition >

After mixing the respective components in the following formulation to prepare a uniform solution, filtration was performed using a nylon filter having a pore size of 0.8 μm to prepare a water-soluble resin composition.

＜＜PVA-1＞＞

15.0 parts by mass of PVA

0.008 parts by mass of surfactant D-1 (described below)

84.9 parts by mass of water

PVA (KURARAAY CO., LTD. manufactured PVA-203 having a saponification degree of 88.0% and a polymerization degree of 300)

＜＜PVP-1＞＞

The following PVP 7.9 parts by mass

0.008 parts by mass of surfactant D-1 (described below)

92.1 parts by mass of water

PVP (Mw 360,000Tokyo Chemical Industry co., ltd. manufactured polyvinylpyrrolidone K90)

< preparation of the Water-insoluble resin composition of comparative example >

＜＜FR-1＞＞

After mixing the respective ingredients in the following formulation to prepare a uniform solution, filtration was performed using a polypropylene filter having a pore size of 0.6 μm to prepare a water-insoluble resin composition.

CYTOP (registered trademark) CTL-809AP 2: ASAHI GLASS CO., LTD. 4.0 parts by mass

Sumitomo 3M Limited Fluorinert FC 7796.0 parts by mass

< preparation of photosensitive resin composition >

Each acid-reactive resin was synthesized in the following manner.

Synthesis of acid-reactive resin A-1

< Synthesis of acid-reactive resin A-1(Mw ═ 25,000) >

PGMEA (propylene glycol monomethyl ether acetate) (32.62g) was placed in a 200mL three-necked flask equipped with a nitrogen inlet tube and a cooling tube, and the temperature was raised to 86 ℃. To this solution, BzMA (16.65g), THFMA (21.08g), t-BuMA (5.76g) and V-601(1.0686g) were dissolved in PGMEA (32.62g) and added dropwise over 2 hours to obtain a compound. Then, the reaction solution was stirred for 2 hours to complete the reaction. The reaction solution was reprecipitated in heptane to yield white powder, which was recovered by filtration, thereby obtaining acid-reactive resin a-1. In the obtained resin, the total protection ratio of THFMA and t-BuMA monomer was 65 mol%, the weight average molecular weight was 25,000, and the dissolution rate was 100 nm/s. The amount of the component having an Mw of 1,000 or less was 3% by mass.

Synthesis of acid-reactive resin A-2

< Synthesis of acid-reactive resin A-2(Mw 57,000) >

PGMEA (32.62g) was placed in a 200mL three-necked flask equipped with a nitrogen inlet tube and a cooling tube, and the temperature was raised to 86 ℃. To this solution, BzMA (16.65g), THFMA (21.08g), t-BuMA (5.76g) and V-601(0.2157g) were dissolved in PGMEA (32.62g) and added dropwise over 2 hours to obtain a compound. Then, the reaction solution was stirred for 2 hours to complete the reaction. The reaction solution was reprecipitated in heptane to yield white powder, which was recovered by filtration, thereby obtaining acid-reactive resin a-2. In the obtained resin, the total protection ratio of THFMA and t-BuMA monomer was 65 mol%, the weight average molecular weight was 57,000, and the dissolution rate was 19 nm/s. The amount of the component having an Mw of 1,000 or less was 4% by mass.

< Synthesis of acid-reactive resin A-3 >

< Synthesis of acid-reactive resin A-3(Mw ═ 9,000) >

PGMEA (32.62g) was placed in a 200mL three-necked flask equipped with a nitrogen inlet tube and a cooling tube, and the temperature was raised to 86 ℃. To this solution, BzMA (16.65g), THFMA (21.08g), t-BuMA (5.76g) and V-601(2.2622g) were dissolved in PGMEA (32.62g) and added dropwise over 2 hours to obtain a compound. Then, the reaction solution was stirred for 2 hours to complete the reaction. The reaction solution was reprecipitated in heptane to yield white powder, which was recovered by filtration, thereby obtaining acid-reactive resin a-3. In the obtained resin, the total protection ratio of THFMA and t-BuMA monomer was 65 mol%, the weight average molecular weight was 9,000, and the dissolution rate was 432 nm/s. The amount of the component having an Mw of 1,000 or less was 3% by mass.

Synthesis of acid-reactive resin A-4

PGMEA (32.62g) was placed in a 200mL three-necked flask equipped with a nitrogen inlet tube and a cooling tube, and the temperature was raised to 86 ℃. To this solution, BzMA (16.65g), THFMA (21.08g), t-BuMA (5.76g) and V-601(1.9329g) were dissolved in PGMEA (32.62g) and added dropwise over 2 hours to obtain a compound. Then, the reaction solution was stirred for 2 hours to complete the reaction. The reaction solution was reprecipitated in heptane to yield white powder, which was recovered by filtration, thereby obtaining acid-reactive resin a-4. The cyclic ether ester protection ratio of the obtained resin was 50 mol%, the weight average molecular weight was 15,000, and the dissolution rate was 200 nm/s. The amount of the component having an Mw of 1,000 or less was 3% by mass.

Synthesis of acid-reactive resin A-5

PGMEA (32.62g) was placed in a 200mL three-necked flask equipped with a nitrogen inlet tube and a cooling tube, and the temperature was raised to 86 ℃. To this solution, BzMA (16.65g), THFMA (21.08g), t-BuMA (5.76g) and V-601(0.3060g) were dissolved in PGMEA (32.62g) and added dropwise over 2 hours to obtain a compound. Then, the reaction solution was stirred for 2 hours to complete the reaction. The reaction solution was reprecipitated in heptane to yield white powder, which was recovered by filtration, thereby obtaining acid-reactive resin a-5. In the obtained resin, the total protection ratio of THFMA and t-BuMA monomer was 65 mol%, the weight average molecular weight was 50,000, and the dissolution rate was 32 nm/s. The amount of the component having an Mw of 1,000 or less was 3% by mass.

Synthesis of acid-reactive resin A-6

PGMEA (propylene glycol monomethyl ether acetate) (32.62g) was placed in a 200mL three-necked flask equipped with a nitrogen inlet tube and a cooling tube, and the temperature was raised to 86 ℃. To this solution, BzMA (21.41g), THFMA (18.97g), t-BuMA (3.84g) and V-601(1.0686g) were dissolved in PGMEA (32.62g) and added dropwise over 2 hours to give a compound. Then, the reaction solution was stirred for 2 hours to complete the reaction. The reaction solution was reprecipitated in heptane to yield white powder, which was recovered by filtration, thereby obtaining acid-reactive resin a-6. In the obtained resin, the total protection ratio of THFMA and t-BuMA monomer was 55 mol%, the weight average molecular weight was 25,000, and the dissolution rate was 188 nm/s. The amount of the component having an Mw of 1,000 or less was 3% by mass.

< Synthesis of acid-reactive resin A-7 >

PGMEA (propylene glycol monomethyl ether acetate) (32.62g) was placed in a 200mL three-necked flask equipped with a nitrogen inlet tube and a cooling tube, and the temperature was raised to 86 ℃. To this solution, BzMA (7.14g), THFMA (27.41g), t-BuMA (7.68g) and V-601(1.0686g) were dissolved in PGMEA (32.62g) and added dropwise over 2 hours to obtain a compound. Then, the reaction solution was stirred for 2 hours to complete the reaction. The reaction solution was reprecipitated in heptane to yield white powder, which was recovered by filtration, thereby obtaining acid-reactive resin a-7. In the obtained resin, the total protection ratio of THFMA and t-BuMA monomer was 85 mol%, the weight average molecular weight was 25,000, and the dissolution rate was 31 nm/s. The amount of the component having an Mw of 1,000 or less was 3% by mass.

The components were mixed in the formulation described in table 1 or table 2 to prepare a uniform solution, which was then filtered using a nylon filter having a pore size of 0.45 μm to prepare a photosensitive resin composition. The details of each component are shown in table 1 or table 2.

< fabrication of organic semiconductor substrate >

An organic semiconductor coating liquid (composition for forming an organic semiconductor) containing the following composition was spin-coated on a circular glass substrate and dried at 130 ℃ for 10 minutes, thereby forming an organic semiconductor layer. The film thickness was 150 nm.

Composition of organic semiconductor coating liquid

P3HT (manufactured by Sigma-Aldrich Co. LLC) 10% by mass%

PCBM (manufactured by Sigma-Aldrich Co. LLC) 10% by mass%

Chloroform (manufactured by Wako Pure Chemical Corporation) 80% by mass

< formation of Water-soluble resin layer >

A water-soluble resin composition was spin-coated on the surface of the above organic semiconductor layer and dried at 100 ℃ for 1 minute, thereby forming a water-soluble resin layer having a thickness of 2 μm.

< evaluation of dissolution Rate >

The photosensitive resin composition was applied to a quartz crystal microbalance (electrode of QCM) as a substrate and heated at 100 ℃ for 1 minute, thereby forming a film (photosensitive layer) having a thickness of 2 μm. The dissolution rate of butyl acetate at 23 ℃ was calculated from the time of dissolution of a 2 μm thick coating film by QCM (relative index).

A: a speed per second of 50nm or more and a speed per second of 150nm or less

B: a speed per second of 20nm to less than 50nm, or a speed per second of more than 150nm to 200nm

C: the second speed is less than 20nm or more than 200nm

< measurement of Metal ion amount >

For the measurement of the total content of sodium ions, potassium ions and calcium ions in the photosensitive resin composition, the metal content in the composition was measured on a scale of 1ppt to 1000ppb by ICP-MS (inductively coupled plasma mass spectrometry) after the liquid preparation.

< side amount of Water content >

After conditioning, the water content of the composition was measured using a karl fischer moisture meter in the composition.

< measurement of static contact Angle >

The measurement of the static contact angle of the photosensitive resin composition with the water-soluble resin layer was performed as follows. That is, a contact angle of a droplet was measured by dropping a water droplet having a droplet size of 10 μ L by a syringe using a static contact angle meter (manufactured by Kyowa Interface Science co., ltd.).

< photolithography of line patterns >

A photosensitive resin composition (resist) was coated on the water-soluble resin layer prepared above, and dried (prebaked) at 100 ℃ for 1 minute to form a photosensitive layer. The film thickness was 2 μm. Next, exposure was performed using a parallel exposure machine through a binary mask made of quartz glass having a mask size of 2 μm and a half pitch of 2 μm by a light source shown in Table 1 or Table 2 so as to obtain an exposure amount shown in Table 1 or Table 2. Then, post baking (PEB) was performed under the conditions shown in table 1 or table 2, and development was performed using butyl acetate at the development treatment time shown in table 1 or table 2. After the development, 4 lines having a width of 2 μm and the number of lines disappeared by the over-development in the space pattern (L/S) were counted.

The results are shown in table 1 or table 2. Here, the absence of a pattern means that the dissolution rate of the 2 μm pattern is low and the analysis is not performed. No peeling means that no pattern disappears.

< coefficient of excessive development >

The overexpansion coefficient in the lithography of the above-described line pattern was measured.

The excessive development coefficient was calculated from the following equation.

The over-development coefficient is [ development processing time (s)/[ (film thickness (nm)/dissolution rate (nm/sec)) of photosensitive layer ]

< evaluation of adhesion of island-shaped pattern >

A photosensitive resin composition (resist) was coated on the water-soluble resin layer prepared above, and dried (prebaked) at 100 ℃ for 1 minute to form a photosensitive layer. The film thickness was 2 μm. Next, exposure was performed using a parallel exposure machine with an exposure amount such that 25 patterns of 1 μm square were formed, using a light source shown in Table 1 or Table 2. Then, post baking (PEB) was performed under the conditions shown in table 1 or table 2, and development was performed using butyl acetate at the development treatment time shown in table 1 or table 2. The number of peeled patterns in the obtained 25 patterns was confirmed.

[ Table 1]

[ Table 2]

The details of the above table are as follows.

PEB: post-baking treatment conditions

Exposure: an exposure light source for development is described.

The method comprises the following steps: indicating the adoption of the conforming item

< acid Generator >

B-1

[ chemical formula 13]

< basic Compound >

C-1

[ chemical formula 14]

C-2

2, 6-diisopropylaniline (primary amine, manufactured by Tokyo Chemical Industry Co., Ltd.)

< surfactant >

D-1: manufactured by OMNOVA SOLUTIONS INC., PF6320

[ chemical formula 15]

D-2

MEGAFACE F-430, manufactured by DIC CORPORATION

< solvent >

E-1: propylene Glycol Monomethyl Ether Acetate (PGMEA)

E-2: 3-Ethoxypropionic acid ethyl ester

From the above results, when the dissolution rate of the photosensitive layer was too high, pattern collapse was significant (comparative example 1). In addition, when the dissolution rate of the photosensitive layer was too low, no pattern was formed (comparative example 2). When the static contact angle between the photosensitive resin composition and the water-soluble resin layer is too large, the line itself and the periphery thereof are peeled off after development even if the dissolution rate is within a predetermined range (comparative example 3). On the other hand, by setting the dissolution rate of the photosensitive layer within an appropriate range, undercut can be reduced, pattern collapse can be suppressed, and the adhesiveness is also excellent.

A photosensitive resin composition using C-2(2, 6-diisopropylaniline, manufactured by Tokyo Chemical Industry co., ltd.) instead of the basic compound C-1 of example 1, a photosensitive resin composition using D-2(MEGAFACE F-430, manufactured by DIC CORPORATION) instead of the surfactant D-1, and a photosensitive resin composition using E-1: E-2 (ethyl 3-ethoxypropionate) ═ 70: 30 (mass ratio) of a mixed solvent in place of the solvent E-1, 25.18:0.16 (mass ratio) of the resin to the acid generator, and 24.98:0.36 (mass ratio). Samples of laminates were produced using each photosensitive resin composition. As a result of evaluating the over-development coefficient, the lithography property, and the adhesion property for each sample, good results were obtained for any substrate.

Description of the symbols

1-photosensitive layer, 2-water-soluble resin layer, 3-organic semiconductor layer, 4-substrate, 5-removing part.

Claims

1. A photosensitive layer contained in a laminate having a water-soluble resin layer and a photosensitive layer,

the photosensitive layer is formed of a photosensitive resin composition containing a compound that generates an acid by irradiation with an activating light ray or a radiation ray, and a resin that changes the dissolution rate of butyl acetate by the action of the acid, the resin that changes the dissolution rate of butyl acetate by the action of the acid is a hydrophobic resin that is soluble in butyl acetate at 23 ℃, the resin has a weight average molecular weight of 10,000 to 50,000, and 50 to 100 mol% of groups soluble in an aqueous alkali solution in all structural units are protected by a hydrophobic protecting group,

2. The photosensitive layer of claim 1, wherein,

the photosensitive layer has a photosensitive ability to i-ray irradiation.

3. The photosensitive layer of claim 1 or 2, wherein,

the content of water in the photosensitive resin composition is 0.01-1% by mass.

4. The photosensitive layer of any one of claims 1 to 3,

the change in dissolution rate is a decrease in dissolution rate.

5. The photosensitive layer of any one of claims 1 to 4,

the resin contained in the photosensitive layer has a structural unit represented by the following formula (1),

6. The photosensitive layer of any one of claims 1 to 5,

the total content of sodium ions, potassium ions, and calcium ions in the photosensitive resin composition is 1 mass ppt to 1000 mass ppb.

7. A photosensitive layer according to any one of claims 1 to 6 for use in organic semiconductor layer processing.

8. A laminate having the photosensitive layer and the water-soluble resin layer described in any one of claims 1 to 7.

9. The laminate according to claim 8, further comprising an organic semiconductor layer, wherein the laminate is formed by laminating the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer in this order.

10. The laminate according to claim 8 or 9,

the resin whose dissolution rate of butyl acetate changes by the action of an acid is a mixture of a resin having a high dissolution rate of butyl acetate and a resin having a low dissolution rate of butyl acetate.

11. A photosensitive resin composition for forming a photosensitive layer, wherein,

the photosensitive layer is a layer which is combined with a water-soluble resin layer to form a laminate, and the dissolution rate when the photosensitive layer which is not exposed to light is immersed in butyl acetate is 20nm/s to 200nm/s,

the photosensitive resin composition contains a compound which generates an acid by irradiation of an activating light or a radiation ray, and a resin which changes the dissolution rate of butyl acetate by the action of the acid,

the resin which changes the dissolution rate of butyl acetate by the action of an acid is a hydrophobic resin soluble in butyl acetate, has a weight average molecular weight of 10,000 to 50,000, protects 50 to 100 mol% of all structural units of groups soluble in an aqueous alkali solution by a hydrophobic protective group, and has a static contact angle of 60 DEG or less on the water-soluble resin layer.

12. The photosensitive resin composition according to claim 11, which is used for organic semiconductor layer processing.

13. A kit for forming a water-soluble resin layer and a photosensitive layer in this order, the kit comprising the photosensitive resin composition according to claim 11 or 12 and a water-soluble resin composition.

14. The kit of claim 13, for use in organic semiconductor layer processing.