Laminate

Abstract

To provide a manufacturing method capable of further improving lithography characteristics of a pattern when forming a side wall or a top plate part of a hollow structure and stably manufacturing the hollow structure, and to provide a laminate useful for the manufacturing method.SOLUTION: In the method for manufacturing a hollow structure comprising a recess 15 and a top plate for closing the opening face of the recess 15, at least one of a side wall 20 and the top plate is formed using a laminate 80 of a support 50 and a resist layer 30. The support 50 is composed of a polyethylene terephthalate film having a light transmission of 85% or more at 365nm wavelengths and a haze value of 1.0% or less when irradiated with 365nm wavelengths, the resist layer 30 is composed of a photosensitive layer formed from a negative photosensitive composition, and a production method is employed in which the resist layer 30 is exposed through the support 50 and the exposed laminate 80 is developed with an organic solvent-containing developer to form a negative pattern.SELECTED DRAWING: Figure 2A

Description

[Technical Field]

[0001] The present invention relates to a method for producing a hollow structure and a laminate useful in this production method. This application claims priority based on Japanese Patent Application No. 2022-023281, filed on February 17, 2022, the contents of which are incorporated herein by reference. [Background technology]

[0002] In recent years, the development of microelectronic devices such as surface acoustic wave (SAW) filters has progressed. The packages that encapsulate such electronic devices have a hollow structure to ensure the propagation of surface acoustic waves and the mobility of the moving parts of the electronic devices. A photosensitive composition is used to form the hollow structure, and the package is manufactured by molding the wiring substrate on which the electrodes are formed while maintaining the hollow structure.

[0003] For example, Patent Document 1 discloses a hollow structure having a hollow portion consisting of an element mounted on a substrate, a side wall provided on the upper part of the substrate so as to surround the outer periphery of the element, and a top plate provided in contact with the upper surface of the side wall and covering the upper part of the element, and a method for manufacturing a hollow package in which this is sealed.

[0004] The hollow structure is manufactured as follows. A dry film resist consisting of a base film (support), a photosensitive layer, and a cover film laminated in that order is used, and the cover film is peeled off from this, which is then laminated onto a substrate, followed by selective exposure, post-exposure baking, development, and heat treatment to create the side walls. Next, a dry film resist with the cover film peeled off is laminated onto the substrate on which the side walls have been created, and the top plate is created by selective exposure, post-exposure baking, development, and hard baking processes, thereby producing a hollow structure with a hollow section. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2020 / 137610 Summary of the Invention [Problem to be solved by the invention]

[0006] In the manufacture of the hollow structure, there is a problem that the film-like top plate portion is easily deformed by the baking treatment when the hollow portion is formed. Furthermore, as electronic components having hollow structures become increasingly smaller and denser, forming patterns with finer dimensions is becoming increasingly important in forming hollow portions. In response to this, conventional photosensitive compositions such as those described in Patent Document 1 are required to have further improved lithography properties for the patterns.

[0007] The present invention has been made in consideration of the above circumstances, and has an object to provide a method for manufacturing a hollow structure, which can further improve the lithography characteristics of a pattern when forming the side wall or top plate portion of the hollow structure, and which can stably manufacture a hollow structure, and a laminate useful for this manufacturing method. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a method for manufacturing a hollow structure comprising a substrate and a recess surrounded by a sidewall formed on the substrate, and a top plate portion covering the opening of the recess, the method comprising the steps of: obtaining the recess with a sidewall formed on the substrate; and forming the top plate portion on the sidewall to obtain a hollow structure; at least one of the sidewall and the top plate portion is formed using a laminate of a support and a resist layer, the support being made of a polyethylene terephthalate film having a light transmittance of 85% or more at a wavelength of 365 nm and a haze value of 1.0% or less when irradiated with light at a wavelength of 365 nm, and the resist layer being a photosensitive layer formed from a negative-type photosensitive composition; and when forming at least one of the sidewall and the top plate portion using the laminate, the resist layer is exposed to light through the support, and the exposed laminate is developed with a developer containing an organic solvent to form a negative-type pattern.

[0009] A second aspect of the present invention is a laminate of a support and a resist layer, wherein the support is made of a polyethylene terephthalate film having a light transmittance of 85% or more at a wavelength of 365 nm and a haze value of 1.0% or less when irradiated with light at a wavelength of 365 nm, and the resist layer is made of a photosensitive layer formed from a negative photosensitive composition, and the laminate is for producing a hollow structure comprising a recess surrounded by a substrate and a sidewall formed on the substrate, and a top plate portion covering the opening of the recess. [Effects of the Invention]

[0010] According to the present invention, it is possible to further improve the lithography characteristics of the pattern when forming the side wall or top plate portion of the hollow structure, and it is possible to provide a method for manufacturing a hollow structure that can stably manufacture the hollow structure, and a laminate useful for this manufacturing method. [Brief explanation of the drawings]

[0011] [Figure 1]FIG. 1 is a schematic diagram illustrating step (i) in one embodiment of a method for producing a hollow structure, and is a side cross-sectional view showing an example of a substrate having a recess on its surface. [Figure 2A] 2A to 2E are schematic diagrams illustrating step (ii) in one embodiment of the method for producing a hollow structural body. Fig. 2A is a diagram illustrating step (ii-1). [Figure 2B] FIG. 2B is a diagram illustrating step (ii-2). [Figure 2C1] FIG. 2C1 is a diagram illustrating step (ii-3). [Figure 2C2] FIG. 2C2 is a diagram showing the state after step (ii-3). [Figure 2D] FIG. 2D is a diagram illustrating step (ii-4). [Figure 2E] FIG. 2E is a diagram illustrating step (ii-5). [Figure 3] This is a photograph of a cross section of a negative pattern in the height direction, showing the evaluation criteria for evaluating the negative pattern shape. In this photograph, the state on the left is graded A, and the state on the right is graded B. [Figure 4] This is a photograph of the line surface of a negative pattern, showing the evaluation criteria for evaluating defects on the surface of a negative pattern. In this photograph, the left side shows the surface roughness of the pattern (X), and the right side shows the surface roughness of the pattern (Y). DETAILED DESCRIPTION OF THE INVENTION

[0012] In this specification and claims, the term "aliphatic" is a relative concept to aromatic, and is defined to mean a group or compound that does not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The term "fluorinated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrase "optionally substituted" includes both cases where a hydrogen atom (-H) is replaced with a monovalent group and where a methylene group (-CH2-) is replaced with a divalent group. The term "exposure" is a general concept that includes irradiation with radiation.

[0013] (Method for manufacturing hollow structure) A first aspect of the present invention is a method for manufacturing a hollow structure comprising a recess surrounded by a substrate and a sidewall formed on the substrate, and a top plate portion covering the opening surface of the recess, the method comprising a step of obtaining the recess with a sidewall formed on a substrate (hereinafter this step will be referred to as "step (i)"), and a step of forming the top plate portion on the sidewall to obtain a hollow structure (hereinafter this step will be referred to as "step (ii)"). In the method for manufacturing a hollow structural body according to the first aspect, at least one of the side wall and the top plate portion is formed using a laminate of a support and a resist layer. When forming at least one of the side wall and the top plate portion using the laminate, the resist layer is exposed through the support, and the exposed laminate is developed with a developer containing an organic solvent to form a negative pattern.

[0014] <Laminate> In the method for producing a hollow structure according to this embodiment, a laminate of a specific support and a resist layer is used. In one embodiment of the laminate, the support constituting the laminate is made of a polyethylene terephthalate film having a light transmittance of 85% or more at a wavelength of 365 nm and a haze value of 1.0% or less when irradiated with light at a wavelength of 365 nm. In one embodiment of the laminate, the resist layer constituting the laminate is made of a photosensitive layer formed from a negative photosensitive composition.

[0015] ≪Support≫ The support constituting the laminate of this embodiment is made of a polyethylene terephthalate film. In this specification and claims, the light transmittance of the support is determined by measuring the total light transmittance (%) in the wavelength range of 200 to 800 nm using an ultraviolet-visible-near-infrared spectrophotometer, and calculating the light transmittance (%) at a wavelength of 360 nm. The support constituting the laminate of this embodiment has a light transmittance of 85% or more for light having a wavelength of 365 nm. The higher the light transmittance for light having a wavelength of 365 nm, the more preferable it is.

[0016] In this specification and claims, the haze value of the support is measured using a haze meter according to a method in accordance with JIS K 7361-1, and the haze value (%) is determined when irradiated with light at a wavelength of 365 nm. The support constituting the laminate of this embodiment has a haze value of 1.0% or less, preferably 0.90% or less, when irradiated with light having a wavelength of 365 nm. The lower the haze value when irradiated with light having a wavelength of 365 nm, the more preferable it is.

[0017] If a support made of a polyethylene terephthalate film has a light transmittance of 85% or more at a wavelength of 365 nm and a haze value of 1.0% or less when irradiated with light at a wavelength of 365 nm, optical effects can be suppressed and the lithography characteristics of the pattern (shape, reduction of defects) can be further improved.

[0018] The thickness of the support constituting the laminate of this embodiment is not particularly limited, and may be, for example, in the range of 10 μm to 200 μm, or may be in the range of 20 μm to 100 μm.

[0019] <Resist layer> The resist layer constituting the laminate of this embodiment is a photosensitive layer formed from a negative photosensitive composition. The negative photosensitive composition preferably contains an epoxy group-containing compound and a cationic polymerization initiator. The details of the composition of such a negative photosensitive composition will be described later. The thickness of the resist layer constituting the laminate of this embodiment is not particularly limited, and may be, for example, in the range of 1 μm to 100 μm, or may be in the range of 5 μm to 50 μm.

[0020] The laminate of the present embodiment described above includes a specific support, i.e., a polyethylene terephthalate film having a transmittance of 85% or more at a wavelength of 365 nm and a haze value of 1.0% or less when irradiated with light having a wavelength of 365 nm, thereby suppressing optical effects when forming the sidewall or top plate of the hollow structure, thereby enabling further improvement in the lithography characteristics of the pattern (shape, reduction of defects). Such a laminate is suitable as a material for manufacturing a hollow structure comprising a recess surrounded by a substrate and a sidewall formed on the substrate, and a top plate portion that closes the opening of the recess. That is, such a laminate is suitable as a material for manufacturing a hollow structure comprising a recess surrounded by a substrate and a sidewall formed on the substrate, and a top plate portion that closes the opening of the recess.

[0021] Such a laminate can have a cover film on the surface of the resist layer opposite the support, thereby forming a dry film resist. The cover film may be a known film, such as a polyethylene terephthalate film, a polyethylene film, or a polypropylene film. The cover film is preferably a film whose adhesive strength with the photosensitive film is weaker than that of the support film. The thickness of the cover film is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 50 μm. The support film and the cover film may be made of the same film material or different film materials. When using the dry film resist, for example, the cover film can be peeled off and the resist layer can be used as a laminate of the support and the resist layer.

[0022] Hereinafter, one embodiment of a method for manufacturing a hollow structural body will be described with reference to the drawings. Fig. 1 is a schematic diagram illustrating step (i), showing an example of a substrate having recesses on its surface, and Figs. 2A to 2E are schematic diagrams illustrating step (ii).

[0023] [Process (i)] In step (i), a sidewall is formed on a substrate, and a recess (a substrate having a recess on its surface) surrounded by the substrate and the sidewall formed on the substrate is obtained. Examples of substrates having recesses on their surfaces include structures in which a recessed pattern is formed on a substrate, stepped substrates, etc. Substrates having recesses on their surfaces can be manufactured by the methods described below. Alternatively, ready-made products may be used as substrates having recesses on their surfaces. The recesses may be made of an organic material or an inorganic material.

[0024] When the recesses are made of an organic material, a substrate having recesses on its surface can be produced by a method including, for example, a step of forming a photosensitive film on a substrate using a negative photosensitive composition (hereinafter referred to as a "film formation step"), a step of exposing the photosensitive film (hereinafter referred to as an "exposure step"), and a step of developing the exposed photosensitive film with a developer containing an organic solvent to form a negative pattern that will become the sidewalls of the recesses (hereinafter referred to as a "development step"). The method for producing a substrate having recesses on its surface as described above can be carried out as follows.

[0025] Film formation process: First, a negative photosensitive composition is applied onto a substrate by a known method such as spin coating, roll coating, or screen printing, and then baked (post-apply bake (PAB)) for 2 to 60 minutes at a temperature of 50 to 150°C to form a photosensitive film. The film formation process can also be performed by disposing a resist layer (photosensitive layer) previously prepared using a negative photosensitive composition on the substrate. In this case, the lamination conditions are preferably, for example, a temperature of 30 to 100°C, a pressure of 0.1 to 0.5 MPa, and a processing speed of 0.2 to 1.0 m / min.

[0026] The substrate is not particularly limited, and any conventionally known substrate can be used, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed. More specifically, examples of substrates for electronic components include substrates made of metals such as silicon, silicon nitride, titanium, tantalum, lithium tantalate (LiTaO3), niobium, lithium niobate (LiNbO3), palladium, titanium tungsten, copper, chromium, iron, and aluminum, as well as glass substrates. The wiring pattern may be made of a material such as copper, aluminum, nickel, or gold.

[0027] The thickness of the photosensitive film formed from the negative photosensitive composition is not particularly limited, but is preferably about 1 to 100 μm.

[0028] Exposure process: Next, the formed photosensitive film is selectively exposed using a known exposure device, either through a mask (mask pattern) on which a predetermined pattern has been formed, or by direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) as needed, for example, at a temperature of 80 to 150°C for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds.

[0029] The wavelength used for exposure is not particularly limited, and the photosensitive film is selectively irradiated (exposed) with radiation, for example, ultraviolet light having a wavelength of 300 to 500 nm, i-line (wavelength 365 nm), or visible light. The radiation source for these radiations may be a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like. Here, radiation refers to ultraviolet light, visible light, far ultraviolet light, X-rays, electron beams, etc. The radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc. For example, when an ultra-high pressure mercury lamp is used, it is 100 to 2000 mJ / cm. 2 is.

[0030] The exposure method for the photosensitive film may be a normal exposure (dry exposure) carried out in air or an inert gas such as nitrogen, or may be liquid immersion lithography.

[0031] Development process: Next, the exposed photosensitive film is developed with a developer containing an organic solvent (organic developer). After development, a rinse treatment is preferably performed. If necessary, a bake treatment (post-bake) may be performed.

[0032] The organic solvent contained in the organic developer can be appropriately selected from known organic solvents, and specific examples thereof include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.

[0033] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone), etc. Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

[0034] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Pyrene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, milk Examples of the alkyl esters include ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate.Among these, butyl acetate or PGMEA is preferred as the ester solvent.

[0035] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0036] The organic developer may contain known additives as needed. Examples of such additives include surfactants. The surfactants are not particularly limited, but may include, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants. The surfactant is preferably a nonionic surfactant, and more preferably a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant. When a surfactant is added, the amount added is usually 0.001 to 5 mass %, preferably 0.005 to 2 mass %, and more preferably 0.01 to 0.5 mass %, based on the total amount of the organic developer.

[0037] The development process can be carried out by a known development method, such as a method of immersing a substrate in a developer for a certain period of time (dip method), a method of piling up developer on the surface of the substrate by surface tension and leaving it standing for a certain period of time (puddle method), a method of spraying developer onto the surface of the substrate (spray method), or a method of continuously dispensing developer while scanning a developer dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method).

[0038] The rinse treatment (cleaning treatment) using a rinse solution can be carried out by a known rinse method, such as a method of continuously applying the rinse solution onto a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in the rinse solution for a certain period of time (dipping method), or a method of spraying the rinse solution onto the surface of the substrate (spray method). The rinsing treatment is preferably carried out using a rinsing liquid containing an organic solvent.

[0039] 1, by the film forming step, exposure step, and development step in the above-described step (i), sidewalls 20 are formed on substrate 10, and recesses 15 are formed between substrate 10 and sidewalls 20 formed on this substrate 10, i.e., a substrate having recesses 15 on its surface can be manufactured. The shape of the upper surface of sidewall 20 is substantially rectangular in a plan view from above. The thickness (horizontal dimension relative to the substrate 10) and height (vertical dimension relative to the substrate 10) of the side wall 20 can be set appropriately based on the size of the hollow portion, which is determined according to the type of electronic device to be accommodated in the recess 15.

[0040] The negative photosensitive composition used in step (i) to form the side wall 20 preferably contains an epoxy group-containing compound and a cationic polymerization initiator, and may be the same negative photosensitive composition as the photosensitive film used in step (ii) to form the top plate portion, which will be described later. In the step (i), a dry film resist in which a support, a resist layer, and a cover film are laminated in this order can also be used as the material for forming the sidewall 20 in the film forming step. It is preferable to use the above-mentioned laminate (a laminate of a support and a resist layer) for the laminated portion of the support and the resist layer in the dry film resist. When the above-described laminate (a laminate of a support and a resist layer) is used, it is preferable to expose the resist layer through the support without peeling off the support in the exposure step, bake (post-exposure bake (PEB)), and then develop the laminate with a developer containing an organic solvent to form a negative pattern. By performing such a procedure, it is possible to further improve the lithography characteristics of the pattern. Furthermore, the incorporation of foreign matter into the resist layer is prevented, allowing for the stable production of hollow structures.

[0041] [Step (ii)] In step (ii), a top plate portion is formed on the side wall of the substrate having a recess on the surface obtained in step (i), thereby obtaining a hollow structure. One embodiment of step (ii) is a case where the above-mentioned laminate (a laminate of a support and a resist layer) is employed, and an example is a form in which the following steps (ii-1), (ii-2), (ii-3), (ii-4), and (ii-5) are performed in this order. The material used to form the top plate is a dry film resist, which is a laminate (a laminate of a support and a resist layer) with a cover film laminated on the resist layer. In Figure 2A, the cover film has already been peeled off.

[0042] 2A to 2E are schematic diagrams illustrating step (ii). Step (ii) is a form in which the following steps (ii-1), (ii-2), (ii-3), (ii-4), and (ii-5) are performed in this order. FIGS. 2A to 2E are diagrams illustrating steps (ii-1) to (ii-5), respectively. 2A to 2E, a substrate having a recess 15 on its surface is formed by a substrate 10 and a sidewall 20 formed on the substrate 10. When forming the top plate portion, a laminate 80 of a support 50 and a resist layer 30 is used.

[0043] [Process (ii-1)] In step (ii-1), the laminate 80 is placed on the upper surface of the side wall 20 so that the surface of the resist layer 30 of the laminate 80 covers the opening surface of the recess 15 in the substrate 10 (FIG. 2A). The lamination conditions for placing the laminate 80 on the upper surface of the side wall 20 are preferably, for example, a temperature of 30 to 100° C., a pressure of 0.1 to 0.5 MPa, and a processing speed of 0.2 to 1.0 m / min. 2A, the laminate 80 is disposed so as to face the substrate 10 across the sidewall 20. A hollow, sealed space is formed between the substrate 10, the sidewall 20, and the resist layer 30.

[0044] [Step (ii-2)] In step (ii-2), the resist layer 30 is exposed through the support 50 (FIG. 2B). As shown in FIG. 2B, for example, the resist layer 30 is selectively exposed through a photomask 60 on which a predetermined pattern is formed, by using a known exposure device, and the light is transmitted through the support 50.

[0045] The wavelength used for exposure is not particularly limited, and radiation such as ultraviolet light having a wavelength of 300 to 500 nm, i-rays (wavelength 365 nm), or visible light is selectively irradiated (exposed). As the radiation source for these radiations, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc. can be used.

[0046] [Step (ii-3)] In step (ii-3), the exposed resist layer 30 is subjected to a heat treatment, a so-called post-exposure bake (PEB) treatment (FIG. 2C1). In this step (ii), the heat treatment in step (ii-3) is carried out, for example, at a temperature of 80 to 150° C. for 40 to 1200 seconds, preferably 40 to 1000 seconds, and more preferably 60 to 900 seconds. As shown in FIG. 2C1, the PEB treatment in step (ii-3) causes the resist layer 30 after the PEB treatment to be divided into exposed portions 30A and unexposed portions 30B that remain unchanged. After the step (ii-3), the support 50 is peeled off from the resist layer 30 in the laminate 80 (FIG. 2C2).

[0047] [Step (ii-4)] In step (ii-4), the resist layer 30 (exposed portion 30A, unexposed portion 30B) after the PEB treatment is developed to form a negative pattern (exposed portion 30A) (FIG. 2D). The development here can be carried out in the same manner as in the development step in the above-mentioned step (i). After the development, a rinsing treatment is preferably carried out.

[0048] [Step (ii-5)] In step (ii-5), the developed negative pattern (exposed portion 30A) is further hardened by heat treatment to obtain a hollow structure 100 whose top plate portion is made of a hardened body 40 of the resist layer 30 (Figure 2E). In FIG. 2E, the cured body 40 is formed by curing the photosensitive material that forms the sidewall 20 and the resist layer 30 and integrating them into one body. The temperature of the heat treatment in step (ii-5) is, for example, 100°C or higher, preferably 100°C or higher and 250°C or lower, and more preferably 150°C or higher and 200°C or lower. The duration of the heat treatment in step (ii-5) is, for example, 30 minutes or more, preferably 30 minutes or more and 120 minutes or less, and more preferably 30 minutes or more and 90 minutes or less.

[0049] According to the manufacturing method for a hollow structure according to the embodiment, which includes steps (i) and (ii) described above, at least the top plate portion is formed using a laminate of a specific support and a resist layer. When forming the top plate portion, this laminate is used, and exposure is performed through the specific support while the resist layer is laminated on the specific support. This reduces optical effects and makes it possible to further improve the lithography characteristics of the pattern (shape, defect reduction). In addition, since the resist layer is laminated on the specific support when forming the top plate portion, deformation of the top plate portion due to thermal expansion of the air in the hollow portion caused by PEB treatment is suppressed, allowing for more stable manufacturing of hollow structures.

[0050] The hollow structure manufactured by the manufacturing method including the above-mentioned steps (i) and (ii) comprises the recess and a top plate portion that closes the opening of the recess, and is suitable for use as a hollow package used in SAW filters, MEMS, various sensors, etc. The method for manufacturing a hollow structure according to the above embodiment is a method useful for manufacturing an insulating film for forming a semiconductor device.

[0051] In the manufacturing method including steps (i) and (ii) described above, both the sidewalls and the top plate portion, or only the top plate portion, are formed using a laminate of a support and a resist layer. However, this is not limited thereto, and the manufacturing method of the hollow structure according to the first aspect may also be configured to form only the sidewalls using the laminate. In either configuration, optical effects can be suppressed, further improving the lithography characteristics of the pattern, and hollow structures can be manufactured stably. In particular, the configuration in which a laminate of a support and a resist layer is used when forming the top plate portion is preferred because deformation of the top plate portion due to thermal expansion of the air in the hollow portion caused by PEB treatment is suppressed, allowing hollow structures to be manufactured more stably.

[0052] Furthermore, in the manufacturing method having the above-mentioned steps (i) and (ii), a form has been described in which the support 50 is peeled off from the resist layer 30 in the laminate 80 after the PEB treatment in step (ii-3), but this is not limiting, and the manufacturing method of the hollow structure according to the first aspect may also be a form in which the support 50 is peeled off from the resist layer 30 in the laminate 80 after exposure and before the PEB treatment. In this form, air that has thermally expanded inside the hollow portion due to the PEB treatment can be easily discharged to the outside.

[0053] For negative-acting photosensitive compositions: The negative-type photosensitive composition used in the present embodiment (hereinafter, sometimes simply referred to as the “photosensitive composition”) contains an epoxy group-containing compound (hereinafter, sometimes referred to as the “component (A)”) and a cationic polymerization initiator (hereinafter, sometimes referred to as the “component (I)”). When a photosensitive film is formed using such a photosensitive composition and selectively exposed to light, the cationic moiety of component (I) decomposes in the exposed areas of the photosensitive film to generate an acid, which causes ring-opening polymerization of the epoxy groups in component (A), reducing the solubility of component (A) in organic developers. Meanwhile, the solubility of component (A) in the unexposed areas of the photosensitive film remains unchanged in the developer containing an organic solvent, resulting in a difference in solubility in the developer containing an organic solvent between the exposed and unexposed areas of the photosensitive film. Therefore, when the photosensitive film is developed with a developer containing an organic solvent, the unexposed areas are dissolved and removed, forming a negative pattern.

[0054] <Epoxy group-containing compound (A)> In the photosensitive composition used in this embodiment, the epoxy group-containing compound (component (A)) may be a compound having enough epoxy groups in one molecule to form a negative pattern by exposure. Examples of the component (A) include novolac epoxy resins (hereinafter also referred to as "component (A1)"), bisphenol epoxy resins (hereinafter also referred to as "component (A2)"), aliphatic epoxy resins, and acrylic resins. The component (A) may be used alone or in combination of two or more. However, the component (A) does not include those that fall under the category of silane coupling agents.

[0055] <Novolac epoxy resin> Suitable examples of novolac epoxy resins (component (A1)) include epoxy resins represented by the following general formula (anv0).

[0056] [ka] [In the formula, R p1 and R p2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p1 may be the same or different. p2may be the same or different. n1 is an integer of 1 to 5. R EP is an epoxy group-containing group. EP may be the same or different from each other.

[0057] In the formula (anv0), R p1 , R p2 The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group. Among them, R p1 , R p2 As the alkyl group, a hydrogen atom or a linear or branched alkyl group is preferred, a hydrogen atom or a linear alkyl group is more preferred, and a hydrogen atom or a methyl group is particularly preferred. In the formula (anv0), multiple R p1 may be the same or different. p2 may be the same as or different from each other.

[0058] In the formula (anv0), n1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0059] In the formula (anv0), R EP is an epoxy group-containing group. R EP The epoxy group-containing group is not particularly limited, and examples thereof include a group consisting of only epoxy groups; a group consisting of only alicyclic epoxy groups; and a group having an epoxy group or alicyclic epoxy group and a divalent linking group. The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure, which is a three-membered ring ether, and specifically, a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that forms the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl groups. The hydrogen atoms of these alicyclic groups may be substituted with alkyl, alkoxy, or hydroxyl groups. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or the alicyclic epoxy group is linked via the divalent linking group bonded to an oxygen atom (—O—) in the formula.

[0060] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0061] Regarding optionally substituted divalent hydrocarbon groups: Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure.

[0062] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0063] Examples of the aliphatic hydrocarbon group containing a ring in its structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0064] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine rings and thiophene rings. Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene groups or heteroarylene groups); groups in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., groups in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0065] The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent, such as a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, or a carbonyl group.

[0066] The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in its structure as a divalent hydrocarbon group may or may not have a substituent, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms. In the alicyclic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a heteroatom, and the heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O)2-, or -S(=O)2-O-.

[0067] In the aromatic hydrocarbon group as a divalent hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting the hydrogen atom of the alicyclic hydrocarbon group.

[0068] Regarding divalent linking groups containing heteroatoms: The heteroatom in the divalent linking group containing a heteroatom is an atom other than a carbon atom or a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0069] In the divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group); -S-, -S(=O)2-, -S(=O)2-O-, and groups represented by the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 , -[Y 21 -C(=O)-O] m” -Y 22 -or- Y 21 -OC(=O)-Y 22 -, wherein Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m″ is an integer of 0 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, acyl, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. Formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -or- Y 21 -OC(=O)-Y 22 -Medium, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as the "divalent hydrocarbon group which may have a substituent" listed above in the description of the divalent linking group. Y 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or ethylene group is particularly preferred. Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula − [Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, in the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22The group represented by - is a group represented by the formula -Y 21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0070] Among them, R EP The epoxy group-containing group in is preferably a glycidyl group.

[0071] Additionally, suitable examples of the component (A1) include resins having a structural unit represented by the following general formula (anv1):

[0072] [ka] [In the formula, R EP is an epoxy group-containing group. a22 and R a23 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0073] In the formula (anv1), R a22 , R a23 The alkyl group having 1 to 5 carbon atoms is R p1 , R p2 The alkyl group has 1 to 5 carbon atoms. R a22 , R a23 The halogen atom is preferably a chlorine atom or a bromine atom. In the formula (anv1), R EP is R in the above formula (anv0). EP and a glycidyl group is preferred.

[0074] Specific examples of the constitutional unit represented by the formula (anv1) are shown below.

[0075] [ka]

[0076] The component (A1) may be a resin consisting solely of the structural unit (anv1), or it may be a resin containing the structural unit (anv1) in addition to other structural units. Examples of other structural units include structural units represented by the following general formulas (anv2) to (anv3).

[0077] [ka] [In the formula, R a24 R is a hydrocarbon group which may have a substituent. a25 ~R a26 , R a28 ~R a30 R are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. a27 represents an epoxy group-containing group or a hydrocarbon group which may have a substituent.

[0078] In the formula (anv2), R a24 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include a linear or branched alkyl group, and a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc. Among these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0079] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, with an isopropyl group being preferred.

[0080] R a24 When is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0081] R a24 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine rings and thiophene rings. R a24Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (an aryl group or a heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0082] In the formulas (anv2) and (anv3), R a25 ~R a26 , R a28 ~R a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. The alkyl group having 1 to 5 carbon atoms and the halogen atom are each defined as R a22 , R a23 is the same as:

[0083] In the formula (anv3), R a27 R is an epoxy group-containing group or a hydrocarbon group which may have a substituent. a27 The epoxy group-containing group is R EP Similar to R a27 The hydrocarbon group which may have a substituent is R a24 is the same as:

[0084] Specific examples of the structural units represented by the formulae (anv2) to (anv3) are shown below.

[0085] [ka]

[0086] When the component (A1) contains other structural units in addition to the structural unit (anv1), there are no particular limitations on the proportion of each structural unit within the component (A1), but the total amount of structural units having an epoxy group relative to the total amount of all structural units constituting the component (A1) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %.

[0087] Commercially available products of the component (A1) include, for example, novolac epoxy resins such as jER-152, jER-154, jER-157S70, and jER-157S65 (all manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, and EPICLON HP5000 (all manufactured by DIC Corporation), and EOCN-1020 (all manufactured by Nippon Kayaku Co., Ltd.).

[0088] As the component (A1), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition used in this embodiment, the content of the component (A1) is preferably 10 to 40 parts by mass, more preferably 15 to 35 parts by mass, and even more preferably 20 to 30 parts by mass, relative to 100 parts by mass of the total parts by mass of the component (A).

[0089] <Bisphenol-type epoxy resin> The bisphenol-type epoxy resin (hereinafter also referred to as "component (A2)") may be any resin having a structural unit containing a bisphenol skeleton, and among these, solid bisphenol-type epoxy resins are preferred. The solid bisphenol epoxy resin refers to a resin that is solid at 25°C and has a structural unit containing a bisphenol skeleton. The epoxy equivalent of the component (A2) is, for example, preferably 800 g / eq. or more, more preferably 800 to 1200 g / eq., and even more preferably 900 to 1100 g / eq.

[0090] Suitable examples of the component (A2) include epoxy resins represented by the following general formula (abp1):

[0091] [ka] [In the formula, R EP is an epoxy group-containing group. EP may be the same or different. a31 and R a32 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. 31 is an integer between 1 and 50.

[0092] In the formula (abp1), R EP is R in the above formula (anv0). EP and a glycidyl group is preferred. In the formula (abp1), R a31 , R a32 The alkyl group having 1 to 5 carbon atoms in the formula (anv0) is R p1 , R p2 The alkyl groups having 1 to 5 carbon atoms are the same as those in the above. a31 , R a32 are each preferably a hydrogen atom or a methyl group. R a31 , R a32 The fluorinated alkyl group having 1 to 5 carbon atoms in a31 , R a32 Examples of such groups include groups in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with fluorine atoms. In the formula (abp1), na 31 is an integer of 1 to 50, preferably an integer of 4 to 15, and more preferably an integer of 5 to 8.

[0093] Examples of commercially available products that can be used as component (A2) include jER-4005, jER-4007, and jER-4010 (all manufactured by Mitsubishi Chemical Corporation); jER-827, jER-828, jER-834, jER-1001, jER-1002, jER-1003, jER-1055, jER-1007, jER-1009, and jER-1010 (all manufactured by Mitsubishi Chemical Corporation); and EPICLON860, EPICLON1050, EPICLON1051, and EPICLON1055 (all manufactured by DIC Corporation).

[0094] As the component (A2), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition used in this embodiment, the content of the component (A2) is preferably 60 to 90 parts by mass, more preferably 65 to 85 parts by mass, and even more preferably 70 to 80 parts by mass, relative to 100 parts by mass of the total parts by mass of the component (A).

[0095] When the (A1) component and the (A2) component are used in combination, the mass ratio of the (A1) component to the (A2) component, expressed as the (A1) component / (A2) component, is preferably 1 / 9 or more and 5 / 5 or less, more preferably 1 / 9 or more and less than 5 / 5, even more preferably 2 / 8 or more and 4 / 6 or less, and particularly preferably 2 / 8 or more and 3 / 7 or less. If the mass ratio is within the above-mentioned preferred range, the resolution is further improved, and a pattern (sidewall) having high adhesion to the wiring layer is easily formed.

[0096] <Aliphatic epoxy resin> Suitable examples of aliphatic epoxy resins include compounds represented by the following general formula (ta1) (hereinafter, this compound may also be referred to as "component (A3)"):

[0097] [ka] [In the formula, R EPis an epoxy group-containing group. EP may be the same or different from each other.

[0098] In the formula (ta1), R EP is an epoxy group-containing group, and R in the formula (anv0) EP is the same as:

[0099] Commercially available products that can be used as the component (A3) include, for example, the TEPIC series (manufactured by Nissan Chemical Industries, Ltd.), such as TEPIC, TEPIC-VL, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-FL, and TEPIC-UC; and MA-DGIC, DA-MGIC, and TOIC (manufactured by Shikoku Chemical Industries, Ltd.).

[0100] As the component (A3), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition used in this embodiment, the content of the component (A3) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 3.5 parts by mass, relative to 100 parts by mass of the total parts by mass of the component (A).

[0101] The aliphatic epoxy resin also includes a compound containing a partial structure represented by the following general formula (m1) (hereinafter also referred to as "component (m1)").

[0102] [ka] [In the formula, n2 is an integer of 1 to 4. * indicates a bond.]

[0103] In the formula (m1), n2 is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0104] Examples of the component (m1) include compounds in which a plurality of partial structures represented by the general formula (m1) are bonded via a divalent linking group or a single bond. Among these, compounds in which a plurality of partial structures represented by the general formula (m1) are bonded via a divalent linking group are preferred. The divalent linking group here is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Here, the divalent hydrocarbon group which may have a substituent and the divalent linking group which contains a hetero atom are represented by R in the above formula (anv0). EP The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom are the same as those described in (epoxy group-containing group), and among these, the divalent linking group containing a hetero atom is preferred. 21 a group represented by —C(═O)—O—, —C(═O)—OY 21 A group represented by Y - is more preferred. 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or ethylene group is particularly preferred.

[0105] Commercially available aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (manufactured by ADEKA Corporation); CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, CELLOXIDE 8010, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (manufactured by Daicel Corporation); and DENACOL EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX Corporation).

[0106] <Acrylic resin> Examples of the acrylic resin include resins having epoxy group-containing units represented by the following general formulas (a1-1) and (a1-2).

[0107] [ka] [wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. 41 is a divalent hydrocarbon group which may have a substituent. 41 is an integer between 0 and 2. a41 and R a42 are epoxy group-containing groups. 42 is 0 or 1. 41 is (na 43 +1)valent aliphatic hydrocarbon group. 43 is an integer between 1 and 3.

[0108] In the formula (a1-1), the alkyl group having 1 to 5 carbon atoms for R is preferably linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms in R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.

[0109] In the formula (a1-1), Va 41 is a divalent hydrocarbon group which may have a substituent, and R in the formula (anv0) EP Examples of the divalent hydrocarbon groups include the same groups as those explained in the above section, which may have a substituent. Among the above, Va 41The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, still more preferably a linear aliphatic hydrocarbon group, and particularly preferably a linear alkylene group.

[0110] In the formula (a1-1), na 41 is an integer of 0 to 2, with 0 or 1 being preferred.

[0111] In the above formulas (a1-1) and (a1-2), R a41 , R a42 is an epoxy group-containing group, and R in the formula (anv0) EP is the same as:

[0112] In the formula (a1-2), Wa 41 In (na 43 The aliphatic hydrocarbon group having a valence of +1 means a hydrocarbon group that is not aromatic and may be saturated or unsaturated, but is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, and a group formed by combining a linear or branched aliphatic hydrocarbon group with an aliphatic hydrocarbon group containing a ring in its structure.

[0113] In the formula (a1-2), na 43 is an integer of 1 to 3, with 1 or 2 being preferred.

[0114] Specific examples of the structural unit represented by the formula (a1-1) or (a1-2) are shown below. In the following formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R a51 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. a52 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. a53 represents a hydrogen atom or a methyl group. 51 is an integer between 0 and 10. R a51 , R a52 , R a53may be the same or different.

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] Furthermore, the acrylic resin may contain structural units derived from other polymerizable compounds in order to appropriately control the physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; hydroxyalkyl (meth)acrylate ... Examples of suitable polymerizable compounds include (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

[0120] When the acrylic resin has other structural units, the content of the epoxy group-containing units in the resin is preferably 5 to 40 mol %, more preferably 10 to 30 mol %, and even more preferably 15 to 25 mol %.

[0121] In addition to the above-mentioned resins, the epoxy group-containing compound may also be a compound represented by the following chemical formula (A4-1) or a compound represented by the following chemical formula (A4-2). An example of a commercially available product that can be used as the compound represented by the following chemical formula (A4-1) is TECHMORE VG-3101L (manufactured by Printec Co., Ltd.). Examples of commercially available products that can be used as the compound represented by the following chemical formula (A4-2) include Showfree (registered trademark) BATG (manufactured by Showa Denko KK).

[0122] [ka]

[0123] Further, examples of the epoxy group-containing compound include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether; xylitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, inositol pentaglycidyl ether; dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, and inositol hexaglycidyl ether.

[0124] In the photosensitive composition used in this embodiment, the component (A) preferably contains the component (A1) and the component (A2), and among these, a composition containing the component (A1) and a solid bisphenol-type epoxy resin is more preferred, and a composition containing an epoxy resin represented by general formula (anv0) and an epoxy resin represented by general formula (abp1) is even more preferred.

[0125] The polystyrene-equivalent weight average molecular weight of component (A) is preferably 100 to 300,000, more preferably 200 to 200,000, and even more preferably 300 to 200,000. By ensuring that the weight average molecular weight is within this range, peeling from the support (such as a substrate having a wiring layer) is less likely to occur, and the strength of the cured film that is formed is sufficiently increased.

[0126] The content of the component (A) in the photosensitive composition used in the embodiment may be adjusted depending on the film thickness of the photosensitive film to be formed.

[0127] <Cationic Polymerization Initiator (I)> In the photosensitive composition used in this embodiment, the cationic polymerization initiator (component (I)) is a compound that generates cations when irradiated with active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light such as KrF or ArF, X-rays, or electron beams, and the cations can serve as polymerization initiators. Examples of the component (I) include onium borate salts (hereinafter also referred to as "component (I1)") and cationic polymerization initiators other than component (I1) (other cationic polymerization initiators).

[0128] Onium borate salts Onium borate salts (component (I1)) generate a relatively strong acid upon exposure. Therefore, by forming a pattern using a photosensitive composition containing component (I1), sufficient sensitivity can be obtained, resulting in the formation of a good pattern. Furthermore, the use of component (I1) reduces the risk of toxicity and metal corrosion. Suitable examples of the component (I1) include compounds represented by the following general formula (I1).

[0129] [ka] [In the formula, R b01 ~R b04 are each independently an aryl group which may have a substituent, or a fluorine atom; q is an integer of 1 or more; q+ is a q-valent organic cation.

[0130] Anion section In the formula (I1), R b01 ~R b04The aryl group in the formula (I) preferably has 5 to 30 carbon atoms, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples include a naphthyl group, a phenyl group, and an anthracenyl group, with a phenyl group being preferred because of its easy availability. R b01 ~R b04 The aryl group in may have a substituent. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, an alkyl group (preferably a linear or branched alkyl group, preferably having 1 to 5 carbon atoms), or a halogenated alkyl group, more preferably a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms, and particularly preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. When the aryl group has a fluorine atom, the polarity of the anion moiety is enhanced, which is preferable. Among them, R in formula (I1) b01 ~R b04 As each of the groups, a fluorinated phenyl group is preferred, and a perfluorophenyl group is particularly preferred.

[0131] A preferred example of the anion moiety of the compound represented by formula (I1) is tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - );Tetrakis[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - );Difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ); Trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - );Tetrakis(difluorophenyl)borate ([B(C6H3F2)4] - ) etc. Among them, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ) is particularly preferred.

[0132] Cation part In the formula (I1), Q q+Suitable examples of the cation include sulfonium cations and iodonium cations, and organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[0133] [ka] [In the formula, R 201 ~R 207 , and R 211 ~R 212 R each independently represents an aryl group, a heteroaryl group, an alkyl group, or an alkenyl group, which may have a substituent. 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 represents -C(=O)- or -C(=O)-O-. Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. x is 1 or 2. W 201 represents a (x+1)-valent linking group.

[0134] R 201 ~R 207 , and R 211 ~R 212 The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 201 ~R 207 , and R 211 ~R 212Examples of the heteroaryl group in the above formula (I) include those in which some of the carbon atoms constituting the aryl group have been substituted with heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of this heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthene; examples of the substituted heteroaryl group include a group in which one hydrogen atom has been removed from 9H-thioxanthen-9-one. R 201 ~R 207 , and R 211 ~R 212 The alkyl group in the formula (I) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 ~R 212 Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (═O), an aryl group, and groups represented by the following formulas (ca-r-1) to (ca-r-10):

[0135] [ka] [In the formula, R' 201 are each independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group.

[0136] In the above formulas (ca-r-1) to (ca-r-10), R' 201 are each independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group.

[0137] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0138] R' 201 The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R' 201 Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, or rings in which some of the hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with oxo groups, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. R' 201Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic ring (an aryl group: for example, a phenyl group, a naphthyl group, or an anthracenyl group); a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group); a group in which one hydrogen atom has been removed from a ring in which some of the hydrogen atoms constituting the aromatic ring have been substituted with an oxo group or the like (for example, anthraquinone); and a group in which one hydrogen atom has been removed from an aromatic heterocycle (for example, 9H-thioxanthene or 9H-thioxanthen-9-one). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0139] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkane is more preferably a polycycloalkane having a bridged ring polycyclic skeleton, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a fused ring polycyclic skeleton, such as a cyclic group having a steroid skeleton.

[0140] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0141] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0142] An optionally substituted chain alkyl group: R' 201 The chain alkyl group may be either a straight chain or a branched chain. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a heneicosyl group, and a docosyl group. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0143] An optionally substituted chain alkenyl group: R' 201 The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the chain alkenyl groups mentioned above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0144] R' 201 Examples of the substituent in the cyclic group, chain alkyl group or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, an oxo group, the above-mentioned R' 201 Examples of the groups include a cyclic group, an alkylcarbonyl group, and a thienylcarbonyl group.

[0145] Among them, R' 201 is preferably a cyclic group which may have a substituent, or a chain alkyl group which may have a substituent.

[0146] R 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 When they are bonded to each other to form a ring together with the sulfur atom in the formula, they may not contain a heteroatom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(applicable R Nis an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0147] In the formula (ca-3), R 208 ~R 209 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups, they may be bonded to each other to form a ring.

[0148] In the formula (ca-3), R 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 210 The alkyl group in the formula (I) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms.

[0149] In the formula (ca-4) and formula (ca-5), Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. Y 201 The arylene group in R' 201Examples of the aromatic hydrocarbon group in the above formula include groups in which one hydrogen atom has been removed from the aryl groups exemplified above. Y 201 The alkylene group and alkenylene group in R' 201 Examples of the chain alkyl group and chain alkenyl group include groups in which one hydrogen atom has been removed from the groups exemplified above as the chain alkyl group and chain alkenyl group.

[0150] In the above formulas (ca-4) and (ca-5), x is 1 or 2. W 201 is an (x+1)-valent, i.e., a divalent or trivalent linking group. W 201 The divalent linking group in the formula (A1) is preferably a divalent hydrocarbon group which may have a substituent. EP The same groups as the optionally substituted divalent hydrocarbon groups exemplified by W are preferred. 201 The divalent linking group in may be linear, branched, or cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group, or a group consisting of an arylene group alone is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferred. W 201 The trivalent linking group in 201 Examples of the divalent linking group include a group in which one hydrogen atom has been removed from the divalent linking group shown in the formula (1), and a group in which the divalent linking group is further bonded to the divalent linking group shown in the formula (1). 201 The trivalent linking group in the formula (I) is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0151] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0152] [ka]

[0153] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent. The substituent includes the above-mentioned R 201 ~R 207 and R 210 ~R 212 The substituents are the same as those exemplified as the substituents that may be possessed by the group

[0154] As the cation represented by the formula (ca-1), cations represented by the following general formulas (ca-1-25) to (ca-1-35) are also preferred.

[0155] [ka]

[0156] [ka] [In the formula, R' 211 is an alkyl group. hal is a hydrogen atom or a halogen atom.

[0157] As the cation represented by the formula (ca-1), cations represented by the following chemical formulas (ca-1-36) to (ca-1-48) are also preferred.

[0158] [ka]

[0159] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0160] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0161] [ka]

[0162] Specific examples of suitable cations represented by the formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0163] [ka]

[0164] As the cation represented by the formula (ca-5), cations represented by the following general formulas (ca-5-1) to (ca-5-3) are also preferred.

[0165] [ka] [In the formula, R' 212 R' is an alkyl group or a hydrogen atom. 211 is an alkyl group.

[0166] Among the above, the cation part [(Q q+ ) 1 / q ] is preferably a cation represented by general formula (ca-1), more preferably a cation represented by each of formulas (ca-1-1) to (ca-1-48), and even more preferably a cation represented by formula (ca-1-25), (ca-1-29), (ca-1-35), (ca-1-47), or (ca-1-48).

[0167] Specific examples of suitable components (I1) are listed below.

[0168] [ka]

[0169] <Other cationic polymerization initiators> Examples of cationic polymerization initiators other than the component (I1) include compounds represented by the following general formula (I2-1) or (I2-2) (hereinafter referred to as "component (I2)"); and compounds represented by the following general formula (I3-1) or (I3-2) (hereinafter referred to as "component (I3)").

[0170] (I2) Ingredients: The component (I2) is a compound represented by the following general formula (I2-1) or (I2-2). The component (I2) generates a relatively strong acid upon exposure to light, and therefore, when a pattern is formed using a photosensitive composition containing the component (I), sufficient sensitivity is obtained and a good pattern is formed.

[0171] [ka] [In the formula, R b05 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b05 may be the same or different from each other. q is an integer of 1 or more, and Q q+ is a q-valent organic cation.

[0172] [ka] [In the formula, R b06 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b06 may be the same or different from each other. q is an integer of 1 or more, and Q q+ is a q-valent organic cation.

[0173] Anion section In the above formula (I2-1), R b05 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b05 may be the same as or different from each other. R b05The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms. Among them, R b05 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and further preferably a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group.

[0174] The anion moiety of the compound represented by formula (I2-1) is preferably represented by the following general formula (b0-2a).

[0175] [ka] [In the formula, R bf05 nb is a fluorinated alkyl group which may have a substituent. 1 is an integer between 1 and 5.

[0176] In formula (b0-2a), R bf05 The optionally substituted fluorinated alkyl group in R b05 The same applies to the optionally substituted fluorinated alkyl groups listed in the above. In formula (b0-2a), nb 1 is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3.

[0177] In the above formula (I2-2), R b06 is a fluorine atom or a fluorinated alkyl group which may have a substituent. b06 may be the same as or different from each other. R b06 The fluorinated alkyl group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 5. Specific examples include alkyl groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms. Among them, R b06 As the alkyl group, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is more preferred, and a fluorine atom is even more preferred.

[0178] Cation part In formula (I2-1) and formula (I2-2), q is an integer of 1 or more, and Q q+ is a q-valent organic cation. This Q q+ As the Q in the above formula (I1), q+ Among these, cations represented by general formula (ca-1) are preferred, with cations represented by formulas (ca-1-1) to (ca-1-48) being more preferred, and cations represented by formula (ca-1-25), (ca-1-29), (ca-1-35), and (ca-1-47) being even more preferred.

[0179] Specific examples of suitable components (I2) are listed below.

[0180] [ka]

[0181] (I3) Ingredients: The component (I3) is a compound represented by the following general formula (I3-1) or (I3-2).

[0182] [ka] [In the formula, R b11 ~R b12 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom. m is an integer of 1 or more, and M m+ are each independently an m-valent organic cation.

[0183] {Component (I3-1)} Anion section In formula (I3-1), R b12 is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and R' 201 Among the cyclic groups, chain alkyl groups and chain alkenyl groups in the explanation of (1), those which have no substituent or those which have a substituent other than a halogen atom are exemplified. R b12 The alkyl group is preferably a chain alkyl group which may have a substituent other than a halogen atom, or an aliphatic cyclic group which may have a substituent other than a halogen atom. The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10. The aliphatic cyclic group is preferably a group in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like (which may have a substituent other than a halogen atom); or a group in which one or more hydrogen atoms have been removed from camphor, or the like. R b12 The hydrocarbon group may have a substituent other than a halogen atom, and examples of the substituent include R b11 Examples of the substituents include those similar to the substituents other than halogen atoms that may be contained in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in the above formula. The phrase "may have a substituent other than a halogen atom" as used herein not only excludes cases where a substituent consists of only halogen atoms, but also excludes cases where a substituent contains at least one halogen atom (for example, when the substituent is a fluorinated alkyl group).

[0184] Preferred examples of the anion moiety of the component (I3-1) are shown below.

[0185] [ka]

[0186] Cation part In formula (I3-1), M m+ is an m-valent organic cation. M m+ Suitable examples of the organic cation include the same cations as those represented by the general formulas (ca-1) to (ca-5) above, and among these, the cation represented by the general formula (ca-1) above is more preferred. 201 , R 202 , R 203 A sulfonium cation in which at least one of the above is an organic group having 16 or more carbon atoms (aryl group, heteroaryl group, alkyl group, or alkenyl group) which may have a substituent is particularly preferred because it improves resolution and roughness characteristics. The substituents that the organic group may have are the same as those described above, and include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an oxo group (═O), an aryl group, and groups represented by the above formulas (ca-r-1) to (ca-r-10). The number of carbon atoms in the organic group (aryl group, heteroaryl group, alkyl group, or alkenyl group) is preferably 16 to 25, more preferably 16 to 20, and particularly preferably 16 to 18. m+ Suitable organic cations include those represented by the above formulas (ca-1-25), (ca-1-26), (ca-1-28) to (ca-1-36), (ca-1-38), (ca-1-46), and (ca-1-47), and among these, the cation represented by the above formula (ca-1-29) is particularly preferred.

[0187] {Component (I3-2)} Anion section In formula (I3-2), R b11is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom, and R' 201 Among the cyclic groups, chain alkyl groups and chain alkenyl groups in the explanation of (1), those which have no substituent or those which have a substituent other than a halogen atom are exemplified.

[0188] Among these, R b11 As the substituent, an aromatic hydrocarbon group which may have a substituent other than a halogen atom, an aliphatic cyclic group which may have a substituent other than a halogen atom, or a chain alkyl group which may have a substituent other than a halogen atom is preferred. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be connected via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the following general formulas (y-al-1) to (y-al-7). In the following general formulas (y-al-1) to (y-al-7), R in the above formula (I3-2) b11 The bond to V' in the following general formulas (y-al-1) to (y-al-7) is 101 is.

[0189] [ka] [In the formula, V' 101 V' is a single bond or an alkylene group having 1 to 5 carbon atoms. 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.]

[0190] V' 102 The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.

[0191] V' 101 and V' 102 The alkylene group in may be a straight-chain alkylene group or a branched-chain alkylene group, and is preferably a straight-chain alkylene group. V' 101 and V' 102 Specific examples of the alkylene group in the formula (I) include a methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; an ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -CH(CH2CH3)CH2 -, etc.; a trimethylene group (n-propylene group) [-CH2CH2CH2-]; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; a tetramethylene group [-CH2CH2CH2CH2-]; alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and a pentamethylene group [-CH2CH2CH2CH2CH2-]. Also, V' 101 or V' 102 In the above, some methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is represented by R' 201 A divalent group obtained by removing one hydrogen atom from a cyclic aliphatic hydrocarbon group (a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group) is preferred, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferred.

[0192] The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group. The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The chain alkyl group preferably has 1 to 10 carbon atoms, and specific examples thereof include straight-chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched-chain alkyl groups such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0193] R b11 As the aryl group, a cyclic group which may have a substituent other than a halogen atom is preferred. Preferred examples of the anion moiety of the component (I3-2) are shown below.

[0194] [ka]

[0195] Cation part In formula (I3-2), M m+ is an m-valent organic cation, and M in the formula (I3-1) m+ is the same as:

[0196] Furthermore, from the viewpoints of increasing the elasticity of the resin film and facilitating the formation of a fine structure without residue, the component (I) is preferably a cationic polymerization initiator that generates an acid with a pKa (acid dissociation constant) of -5 or less upon exposure. By using a cationic polymerization initiator that generates an acid with a pKa of more preferably -6 or less, and even more preferably -8 or less, it becomes possible to obtain high sensitivity to exposure. The lower limit of the pKa of the acid generated by the component (I) is preferably -15 or more. By using a cationic polymerization initiator that generates an acid with such a suitable pKa, high sensitivity can be easily achieved. Here, "pKa (acid dissociation constant)" refers to a commonly used index indicating the acid strength of a substance of interest. In this specification, pKa is a value at a temperature of 25°C. The pKa value can be determined by measurement using known methods. Alternatively, a calculated value using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development) can also be used.

[0197] Specific examples of suitable components (I3) are listed below.

[0198] [ka]

[0199] As the component (I), one type may be used alone, or two or more types may be used in combination. In the photosensitive composition used in this embodiment, the component (I) is preferably at least one selected from the group consisting of the components (I1), (I2), and (I3).

[0200] In the photosensitive composition used in this embodiment, the content of component (I) is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, even more preferably 0.15 to 3 parts by mass, and particularly preferably 0.2 to 1 part by mass, relative to 100 parts by mass of the total parts by mass of component (A). When the content of component (I) is equal to or greater than the lower limit of the preferred range, sufficient sensitivity is obtained, and the lithography characteristics of the pattern are further improved. In addition, the strength of the cured resin film is further increased. On the other hand, when the content is equal to or less than the upper limit of the preferred range, sensitivity is appropriately controlled, and a pattern with a good shape is easily obtained.

[0201] <Optional ingredients> The photosensitive composition used in this embodiment may contain other components (optional components) as needed, in addition to the above-described components (A) and (I). If desired, the photosensitive composition of the embodiment may contain miscible additives, such as a metal oxide (M), a sensitizer component, a silane coupling agent, a solvent, an additional resin for improving the performance of the film, a dissolution inhibitor, a basic compound, a plasticizer, a stabilizer, a colorant, and an antihalation agent.

[0202] <Metal oxides (M)> In addition to the components (A) and (I), the photosensitive composition used in this embodiment may further contain a metal oxide (M) (hereinafter also referred to as "component (M)"), since this facilitates the formation of a cured film with increased strength. By including component (M), it is possible to form a high-resolution pattern with a good shape. Examples of the component (M) include oxides of metals such as silicon (metallic silicon), titanium, zirconium, hafnium, etc. Among these, silicon oxide is preferred, and among these, it is particularly preferred to use silica. The component (M) is preferably in the form of particles, and the particulate component (M) preferably has a volume average particle diameter of 5 to 40 nm, more preferably 5 to 30 nm, and even more preferably 10 to 20 nm.

[0203] <Sensitizer ingredient> The photosensitive composition used in this embodiment may further contain a sensitizer component. The sensitizer component is not particularly limited as long as it can absorb energy from exposure and transfer that energy to another substance. Specific examples of the sensitizer component that can be used include benzophenone-based photosensitizers such as benzophenone and p,p'-tetramethyldiaminobenzophenone, carbazole-based photosensitizers, acetophenone-based photosensitizers, naphthalene-based photosensitizers such as 1,5-dihydroxynaphthalene, phenol-based photosensitizers, anthracene-based photosensitizers such as 9-ethoxyanthracene, and known photosensitizers such as biacetyl, eosin, rose bengal, pyrene, phenothiazine, and anthrone.

[0204] <Solvent> The photosensitive composition used in this embodiment may further contain a solvent (hereinafter sometimes referred to as "component (S)"). Examples of the component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; monoalkyl ethers or monoalkyl ethers of the above polyhydric alcohols or the above compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether; Examples of suitable organic solvents include derivatives of polyhydric alcohols such as compounds having an ether bond, such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane; and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; and dimethyl sulfoxide (DMSO).

[0205] The component (S) may be used alone or as a mixed solvent of two or more types.

[0206] When component (S) is contained, the amount used is not particularly limited, and is set appropriately depending on the thickness of the coating film at a concentration that allows the photosensitive composition to be applied to a substrate or the like without dripping. For example, the component (S) can be used so that the solid content concentration is 50% by mass or more, or the component (S) can be used so that the solid content concentration is 60% by mass or more. It is also possible to employ an embodiment in which the component (S) is substantially not contained (that is, an embodiment in which the solid content concentration is 100% by mass).

[0207] (Laminate) A second aspect of the present invention is a laminate of a support and a resist layer, wherein the support is made of a polyethylene terephthalate film having a light transmittance of 85% or more at a wavelength of 365 nm and a haze value of 1.0% or less when irradiated with light at a wavelength of 365 nm, and the resist layer is made of a photosensitive layer formed from a negative-type photosensitive composition. The laminate according to the second aspect is for producing a hollow structure comprising a substrate, a recess surrounded by a sidewall formed on the substrate, and a top plate portion that closes the opening of the recess. The explanation of such a laminate is the same as that of the <laminated body> explained in the above (Method for manufacturing a hollow structure). [Example]

[0208] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In this example, the following support and negative photosensitive composition were used.

[0209] ≪Support≫ As the support, the following PET (1) to (7), which are polyethylene terephthalate films each having a thickness of 50 μm, were used. The light transmittance and haze value of the support were measured as follows, and the results are shown in Table 1.

[0210] Light transmittance measurement method: The light transmittance of the support was determined by measuring the total light transmittance (%) in the wavelength range of 200 to 800 nm (baseline correction: air blank) using an ultraviolet-visible-near-infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation), and calculating the light transmittance (%) at a wavelength of 360 nm.

[0211] How to measure haze: The haze value (%) of the support was measured using a haze meter COH7700 (manufactured by Nippon Denshoku Industries Co., Ltd.) according to a method in accordance with JIS K 7361-1, and the haze value (%) was determined when irradiated with light at a wavelength of 365 nm.

[0212] [Table 1]

[0213] <Negative-type photosensitive composition> The components shown in Table 2 were mixed and dissolved, and the mixture was filtered using a PTFE filter (pore size 1 μm, manufactured by PALL Corporation) to prepare a negative photosensitive composition (RN) which was an MEK solution with a solid content of 84% by mass.

[0214] [Table 2]

[0215] In Table 2, the abbreviations have the following meanings: The values ​​in brackets [ ] are the amounts of each component blended (parts by mass; solid content equivalent). (A)-1: A compound represented by the following chemical formula (A1-1), trade name "jER-157S70", manufactured by Mitsubishi Chemical Corporation. (I)-1: A cationic polymerization initiator represented by the following chemical formula (I2-2-2). (D)-1: Sensitizer, α-naphthol. (SC)-1: A compound represented by the following chemical formula (SC-1).

[0216] [ka]

[0217] <Preparation of laminate> A laminate was prepared using the above-mentioned PET (1) to (7) supports and the negative photosensitive composition (RN).

[0218] Example 1 Using PET (1) as a support, a negative photosensitive composition (RN) was applied onto a 50 μm-thick PET (1) using an applicator, and a resist layer was formed by baking at a temperature of 90°C for 5 minutes, thereby producing a laminate of a 50 μm-thick PET (1) and a 20 μm-thick resist layer.

[0219] (Examples 2 to 5, Comparative Examples 1 and 2) Laminates of 50 μm thick PET (2) to (7) and a 20 μm thick resist layer were prepared in the same manner as in Example 1, except that PET (1) was replaced with PET (2) to (7), respectively, as the support.

[0220] As the cover film, a polyethylene terephthalate film (PET(0)) other than PET(1) to (7) was used. Then, the PET(0) was attached to the surface of the resist layer of each of the laminates prepared above, opposite to the support, to prepare a dry film resist.

[0221] <Negative pattern formation> The cover film PET(0) was peeled off from the dry film resist to leave a laminate (a laminate of a support and a resist layer), which was then attached to a Si substrate so that the resist layer was in contact with the Si substrate. The lamination operation was carried out using a laminator at 90°C, a pressure of 0.3 MPa, and a speed of 0.5 m / min.

[0222] Next, the resist layer in the laminate attached to the Si substrate was exposed to 400 mJ / cm2 in i-line equivalent using a ghi broadband exposure machine via a support. 2 The exposure was carried out.

[0223] Next, the exposed laminate was subjected to a baking treatment (PEB: Post exposure bake) at 90° C. for 300 seconds.

[0224] Next, the support was peeled off from the laminate after PEB, and the resist layer after the bake treatment was developed by immersing it in propylene glycol monomethyl ether acetate (PGMEA) at 23°C for 2 minutes to form a negative pattern.

[0225] [Evaluation of negative pattern shape] The shape of the target negative pattern (LS pattern with a line width of 20 μm and a pitch width of 40 μm) formed in the above <Formation of negative pattern> was evaluated according to the following evaluation criteria by observing an SEM image (magnification 1000 times). The results are shown in Table 3 as "shape".

[0226] 3 is a photograph of a cross section of a negative pattern in the height direction, showing the evaluation criteria for evaluating the shape of the negative pattern. In FIG. 3, line portions 90 are formed at a constant interval (pitch). Evaluation criteria A: The side surface 92 of the line portion 90 is smooth and free of roughness B: A state in which slight roughness is observed on the side surface 92 of the line portion 90.

[0227] [Evaluation of defects on negative patterned surfaces] The surface roughness of the target negative pattern (LS pattern with a line width of 20 μm and a pitch width of 40 μm) formed in the above <Formation of negative pattern> was evaluated using an optical microscope (magnification 20x) according to the following evaluation criteria. The results are shown in Table 3 as "Defects".

[0228] FIG. 4 is a photograph of the surface of a line portion of a negative pattern, showing the evaluation criteria for evaluating defects on the surface of a negative pattern. The surface roughness condition (X) of the pattern is good with little surface roughness. The surface roughness of the pattern (Y) is significant and in a poor state. Evaluation criteria A: Pattern surface roughness (X) or similar condition B: State between the surface roughness state (X) and the surface roughness state (Y) of the pattern C: Pattern surface roughness (Y) or similar

[0229] [Table 3]

[0230] From the results shown in Table 3, it was confirmed that when the laminates of Examples 1 to 5 were used, the optical effects were reduced compared to when the laminates of Comparative Examples 1 and 2 were used, and it was possible to further improve the lithography characteristics of the pattern (shape, defect reduction).

[0231] <Manufacturing of hollow structures> The negative photosensitive composition (RN) was uniformly applied onto a Si substrate using an applicator, and baked (PAB) at a heating temperature of 90° C. for 5 minutes to form a photosensitive film (film thickness 20 μm). Next, the photosensitive film was irradiated with 200 mJ / cm 2 using a Suss MABA8 Gen4 pro aligner. 2 The exposure was performed at a dose of 1000 kJ / cm² (ghi broadband). Next, the exposed photosensitive film was post-exposure heated on a hot plate at 90° C. for 5 minutes to obtain a pre-cured film. Next, puddle development was carried out at 23°C for 120 seconds using PGMEA as a developer, and after shaking off and drying, the film was heated at 200°C for 1 hour in a nitrogen atmosphere to be cured. As a result, a recess pattern was formed on the Si substrate, with the periphery of a square measuring 1170 μm in length and 1500 μm in width being surrounded by side walls made of the cured film and each having a width of 50 μm, thereby obtaining a substrate with walls (recesses).

[0232] Next, a laminate consisting of a resist layer made of a photosensitive layer adjusted to a film thickness of 30 μm using the negative photosensitive composition (RN) and a support made of PET (1), a polyethylene terephthalate film with a thickness of 50 μm, was placed (laminated) on the upper surface of the side wall (Wall) so as to cover the opening surface of the recess in the wall-attached substrate. The lamination conditions for placing the laminate on the upper surface of the side wall were a temperature of 90°C, a pressure of 0.3 MPa, and a processing speed of 0.5 m / min. At this time, the laminate was placed so that the resist layer faced the Si substrate via the side wall, forming a hollow, sealed space surrounded by the Si substrate, the side wall, and the resist layer.

[0233] Next, the resist layers constituting the laminate were irradiated with 200 mJ / cm 2 through a predetermined mask pattern using a Suss MABA8 Gen4 pro aligner. 2 Selective exposure (equivalent to i-line) was carried out through the support (PET(1)). Next, the laminate after the selective exposure was subjected to post-exposure heating on a hot plate at a temperature of 90° C. for 5 minutes. Thereafter, the support (PET (1)) was peeled off from the resist layer of the laminate.

[0234] Next, the resist layer after exposure and baking was subjected to puddle development at 23°C for 120 seconds using PGMEA as a developer to form a roof pattern that would become the top plate portion (the roof that covers the opening surface of the recess). The roof pattern was further hardened by heating it in an oven at 200°C for 60 minutes to produce a hollow structure (cavity size: length 1170 μm x width 1500 μm x height 50 μm) in which the side walls and top plate were integrated.

[0235] In the above-mentioned <Manufacturing of hollow structure>, when forming the top plate portion, patterns with fine dimensions were produced with good lithography characteristics (shape, reduced defects), and deformation, etc. was suppressed, allowing the hollow structure to be manufactured stably.

[0236] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Addition, omission, substitution, and other modifications of the configuration are possible within the scope of the spirit of the present invention. The present invention is not limited by the above description, but is limited only by the scope of the appended claims. [Explanation of symbols]

[0237] 10 substrate, 20 sidewall, 30 resist layer, 40 cured body, 50 support, 60 photomask, 80 laminate, 100 hollow structure

Claims

1. A laminate of a support and a resist layer, the support is made of a polyethylene terephthalate film having a light transmittance of 85% or more at a wavelength of 365 nm and a haze value of 1.0% or less when irradiated with light at a wavelength of 365 nm; the resist layer is a photosensitive layer formed from a negative photosensitive composition, The negative photosensitive composition contains an epoxy group-containing compound as a component (A) and a cationic polymerization initiator as a component (I), The component (I) includes at least one compound selected from the group consisting of compounds represented by any one of the following general formulas (I1), (I2-1), (I2-2), (I3-1), and (I3-2): A laminate for manufacturing a hollow structure comprising a substrate, a recess surrounded by a sidewall formed on the substrate, and a top plate portion covering the opening of the recess. 【Chemistry 1】 [In general formula (I1), R ｂ０１ ~R ｂ０４ are each independently an aryl group which may have a substituent, or a fluorine atom. ｂ０５ is a fluorine atom or a fluorinated alkyl group which may have a substituent. ｂ０５ may be the same or different. ｂ０６ is a fluorine atom or a fluorinated alkyl group which may have a substituent. ｂ０６ In general formula (I1), general formula (I2-1) and general formula (I2-2), q is an integer of 1 or more, and Q ｑ＋ are each independently a q-valent organic cation. ｂ１２ is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom. ｂ１１ In general formula (I3-1) and general formula (I3-2), m is an integer of 1 or more, and M is a cyclic group which may have a substituent other than a halogen atom, a chain alkyl group which may have a substituent other than a halogen atom, or a chain alkenyl group which may have a substituent other than a halogen atom. ｍ＋ are each independently an m-valent organic cation.

2. 2. The laminate according to claim 1, wherein the cationic polymerization initiator comprises a compound represented by general formula (I2-2).

3. The laminate according to claim 1 or 2, wherein the epoxy group-containing compound is a novolac type epoxy resin.

4. The thickness of the support is in the range of 20 μm to 200 μm, 3. The laminate according to claim 1, wherein the resist layer has a thickness in the range of 1 μm to 100 μm.

5. 3. The laminate according to claim 1, wherein the content of the component (I) is 0.05 to 5 parts by mass when the total mass of the component (A) is 100 parts by mass.

6. 3. The laminate according to claim 1, wherein the support is made of a polyethylene terephthalate film having a light transmittance of 85% or more at a wavelength of 365 nm and a haze value of 0.90% or less when irradiated with light at a wavelength of 365 nm.

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