JP2014164043A - Pattern forming method and production method of structure including phase separation structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an easy method for forming a guide pattern in a chemical epitaxy process.SOLUTION: A pattern forming method includes the steps of: forming a photosensitive resin film 2 on a support body 1 by using a photosensitive resin composition which generates an acid by exposure and causes changes in the solubility with a developing solution by an action of an acid, then exposing the photosensitive resin film 2, and subjecting the exposed photosensitive resin film to negative development using a developing solution containing an organic solvent to form a pre-pattern comprising the photosensitive resin film 2a; forming a neutralized film 3 containing a surface treating agent on the support body 1 where the pre-pattern is formed; subjecting the pre-pattern and the neutralized film 3 formed on the support body 1 to alkali development so as to remove the pre-pattern from the support body 1 and to form a pattern comprising a neutralized film 3a on the support body 1.

Description

  The present invention relates to a pattern forming method and a method for manufacturing a structure including a phase separation structure.

In recent years, with the further miniaturization of large-scale integrated circuits (LSIs), a technique for manufacturing a more delicate structure is required. In response to such a demand, an attempt to form a finer pattern using a phase separation structure formed by self-assembly of a block copolymer in which incompatible blocks are bonded to each other has begun (for example, , See Patent Document 1).
In order to utilize the phase-separated structure of the block copolymer, it is essential that the self-assembled nanostructure formed by microphase separation is formed only in a specific region and arranged in a desired direction. In order to realize these position control and orientation control, processes such as grapho epitaxy for controlling the phase separation pattern by the guide pattern and chemical epitaxy for controlling the phase separation pattern by the difference in the chemical state of the substrate have been proposed. (For example, refer nonpatent literature 1).

In the chemical epitaxy process, a neutralized film containing a surface treatment agent having affinity with any block constituting the block copolymer is arranged on the substrate surface in a predetermined pattern. The orientation of each phase of the phase separation structure is controlled by the pattern of the neutralization film (guide pattern) arranged on the substrate surface. For this reason, in order to form a desired phase separation structure, it is important to arrange the neutralized film in accordance with the period of the block copolymer. For example, the neutralized film is ultrafinely processed into a line-and-space pattern in which the half pitch corresponds to the period of the block copolymer, so that the phase separation structure of the block copolymer can be changed so that each phase is parallel to each other. It can be oriented on the surface.
A photosensitive resin composition is used for forming the guide pattern.
In the chemical epitaxy process, for example, after forming a neutralized film on the substrate surface, the guide pattern is formed by applying a photosensitive resin composition on the neutralized film to form a photosensitive resin film. The photosensitive resin film is patterned to form a prepattern made of a photosensitive resin film such as line and space, and then the neutralized film exposed in the space portion is removed by etching, and then the prepattern is formed. It is formed by peeling.

JP 2008-36491 A

Proceedings of SPIE, Volume 7637, 76370G-1 (2010).

However, in the conventional chemical epitaxy process, in the formation of the guide pattern, in addition to the formation of the photosensitive resin film, etching and exposure and baking operations are required to peel off the prepattern made of the photosensitive resin film. There is a problem in that a complicated operation is required.
This invention is made | formed in view of the said situation, and makes the subject the simple formation method of the guide pattern in a chemical epitaxy process.

  When forming a guide pattern by a chemical epitaxy process, the present inventors form a neutralized film after first forming a prepattern made of a photosensitive resin film. By forming with negative development using a photosensitive resin composition whose solubility in the developer changes by the action of the above, it becomes possible to peel off the pre-pattern without the need for operations such as exposure and baking, It has been found that a guide pattern can be easily formed without requiring an etching operation, and the present invention has been completed.

  That is, the first aspect of the present invention is to form a photosensitive resin film on a support using a photosensitive resin composition that generates an acid upon exposure and changes its solubility in a developing solution by the action of the acid. (1) forming a pre-pattern by exposing the photosensitive resin film, and negatively developing the exposed photosensitive resin film using a developer containing an organic solvent; A step (2) of forming a neutralized film containing a surface treatment agent on the support on which the pattern is formed, and the pre-pattern and the neutralized film formed on the support are alkali-developed, A step (3) of removing the pre-pattern from the support and forming a pattern comprising the neutralized film on the support.

  In the second aspect of the present invention, a plurality of kinds of patterns are coated on the support on which the pattern comprising the neutralized film is formed by the pattern forming method of the first aspect of the present invention. A structure comprising a phase-separated structure, comprising: a step (4) of forming a layer containing a block copolymer to which a polymer is bonded; and a step (5) of phase-separating the layer containing the block copolymer (5). It is a manufacturing method.

  According to the present invention, a guide pattern can be formed by a simple method in a chemical epitaxy process.

It is a schematic process drawing explaining an example of one embodiment of a pattern formation method concerning the present invention. It is a schematic process drawing explaining an embodiment of a method for producing a structure including a phase separation structure according to the present invention.

In the present specification and claims, “aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
The “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
“Fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms.
“Structural unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When it is described as “may have a substituent”, when a hydrogen atom (—H) is substituted with a monovalent group, and when a methylene group (—CH ₂ —) is substituted with a divalent group And both.
“Exposure” is a concept including general irradiation of radiation.

“A structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
“Acrylic acid ester” is a compound in which the hydrogen atom at the carboxy group terminal of acrylic acid (CH ₂ ═CH—COOH) is substituted with an organic group.
In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α0 ) that replaces the hydrogen atom bonded to the α-position carbon atom is an atom or group other than a hydrogen atom, such as an alkyl group having 1 to 5 carbon atoms or a halogenated group having 1 to 5 carbon atoms. An alkyl group etc. are mentioned. In addition, itaconic acid diesters in which the substituent (R ^α0 ) is substituted with a substituent containing an ester bond, and α-hydroxyacrylic esters in which the substituent (R ^α0 ) is substituted with a hydroxyalkyl group or a group with a modified hydroxyl group thereof Shall be included. The α-position carbon atom of the acrylate ester is a carbon atom to which a carbonyl group of acrylic acid is bonded unless otherwise specified.
Hereinafter, an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylate ester. Further, the acrylate ester and the α-substituted acrylate ester may be collectively referred to as “(α-substituted) acrylate ester”.

The “structural unit derived from acrylamide” means a structural unit formed by cleavage of an ethylenic double bond of acrylamide.
In acrylamide, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and one or both of the hydrogen atoms of the amino group of acrylamide may be substituted with a substituent. The α-position carbon atom of acrylamide is a carbon atom to which the carbonyl group of acrylamide is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom bonded to the α-position carbon atom of acrylamide are the same as those described as the α-position substituent (substituent (R ^α0 )) in the α-substituted acrylic ester. Can be mentioned.

“A structural unit derived from hydroxystyrene or a hydroxystyrene derivative” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene or a hydroxystyrene derivative.
“Hydroxystyrene derivative” is a concept including those in which the hydrogen atom at the α-position of hydroxystyrene is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those in which the hydrogen atom of the hydroxy styrene of the hydroxystyrene which may be substituted with a substituent at the α-position is substituted with an organic group; the hydrogen atom at the α-position is substituted with a substituent The thing etc. which the substituents other than a hydroxyl group couple | bonded with the benzene ring of good hydroxystyrene are mentioned. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same substituents as those mentioned as the substituent at the α-position in the α-substituted acrylic ester.

The “structural unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative” means a structural unit configured by cleavage of an ethylenic double bond of vinyl benzoic acid or a vinyl benzoic acid derivative.
The “vinyl benzoic acid derivative” is a concept including a compound in which the hydrogen atom at the α-position of vinyl benzoic acid is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those in which the hydrogen atom at the carboxy group of vinyl benzoic acid, which may be substituted with a hydrogen atom at the α-position, is substituted with an organic group; the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group and a carboxy group is bonded to the benzene ring of vinyl benzoic acid. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.

“Styrene” is a concept that includes styrene and those in which the α-position hydrogen atom of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.
“Structural unit derived from styrene” and “structural unit derived from styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.

The alkyl group as a substituent at the α-position is preferably a linear or branched alkyl group, specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Specific examples of the halogenated alkyl group as the substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the substituent at the α-position” are substituted with a halogen atom. It is done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as a substituent at the α-position include a group in which part or all of the hydrogen atoms of the “alkyl group as the substituent at the α-position” are substituted with a hydroxyl group. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.

≪Pattern formation method≫
In the first aspect of the present invention, a photosensitive resin film is formed on a support using a photosensitive resin composition that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid. Step (1) of exposing the photosensitive resin film, and negatively developing the exposed photosensitive resin film with a developer containing an organic solvent to form a pre-pattern; and A step (2) of forming a neutralized film containing a surface treatment agent on the formed support, and the pre-pattern and the neutralized film formed on the support are alkali-developed, and the support And a step (3) of removing the pre-pattern from the body and forming a pattern comprising the neutralized film on the support.
Hereinafter, the pattern formation method of this aspect is demonstrated, referring drawings. However, the present invention is not limited to this.

FIG. 1 shows an example of an embodiment of the pattern forming method of this aspect.
In this embodiment, a photosensitive resin composition is used that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid.
First, the support body 1 is prepared (FIG. 1 (a)).
Next, a photosensitive resin film 2 is formed on the support 1 using the photosensitive resin composition (FIG. 1B). Thereafter, the photosensitive resin film 2 is exposed, and the exposed photosensitive resin film is negatively developed using a developer containing an organic solvent. Thereby, the pre-pattern which consists of the some photosensitive resin film 2a spaced apart is formed (FIG.1 (c); above, process (1)).
Next, a neutralized film 3 containing a surface treatment agent is formed on the support 1 on which the prepattern has been formed so as to cover the prepattern (FIG. 1 (d); step (2)).
Next, the pre-pattern and neutralized film 3 formed on the support 1 are alkali-developed. Thus, the pre-pattern is removed from the support 1 and a pattern made of the neutralized film 3a is formed on the support 1 (FIG. 1 (e); step (3)).
As described above, according to the pattern forming method of the present embodiment, in the chemical epitaxy process, it is possible to peel the pre-pattern without the need for operations such as exposure and baking, and the guide without requiring the etching operation. A pattern can be easily formed.

<Step (1)>
In the step (1), a photosensitive resin film is formed on a support using a photosensitive resin composition that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid. The resin film is exposed, and the exposed photosensitive resin film is negatively developed using a developer containing an organic solvent to form a pre-pattern.
The formation of the pre-pattern on the support 1 can be performed as follows, for example.

First, a photosensitive resin composition is applied onto the support 1 with a spinner or the like, and a baking (post-apply bake (PAB)) treatment is performed, for example, at a temperature of 80 to 150 ° C., preferably for 40 to 120 seconds. Preferably, it is applied for 60 to 90 seconds to form the photosensitive resin film 2.
The thickness of the photosensitive resin film 2 is appropriately determined depending on the height of the pattern made of the neutralization film 3a, and is preferably 30 nm or more, and more preferably 40 to 200 nm.
Next, the photosensitive resin film 2 is exposed through a mask (mask pattern) in which a predetermined pattern is formed using an exposure apparatus such as an ArF exposure apparatus, an electron beam drawing apparatus, or an EUV exposure apparatus, or After performing selective exposure by drawing or the like by direct irradiation with an electron beam without passing through a mask pattern, a baking (post-exposure baking (PEB)) treatment is performed, for example, at a temperature of 80 to 150 ° C., preferably for 40 to 120 seconds. More preferably, it is applied for 60 to 90 seconds.
Next, the photosensitive resin film after the selective exposure is negatively developed.
Negative development is carried out using a developer containing an organic solvent (organic developer).
After the negative development, a rinsing process is preferably performed. This rinsing treatment is preferably a treatment using a rinsing liquid containing an organic solvent.
After such a negative development or rinsing process, an organic developer or rinsing liquid adhering to the pre-pattern may be removed with a supercritical fluid.

In this embodiment, after negative development or after rinsing, baking (post-baking) is preferably performed after the negative development. The baking (post-baking) is preferably performed at 180 ° C. or higher, more preferably performed at 190 ° C. or higher, and particularly preferably performed at 200 to 250 ° C. The heating time is preferably 30 to 600 seconds, more preferably 60 to 450 seconds.
By performing baking at a high temperature of preferably 180 ° C. or higher after negative development, resistance to a solvent can be easily imparted to the obtained prepattern. That is, when the neutralized film 3 is formed on the prepattern in the next step (2) by performing the baking, the prepattern is formed of the solvent contained in the surface treatment agent for forming the neutralized film. Less affected.

The type of the support 1 is not particularly limited as long as the photosensitive resin composition can be applied on the surface thereof. For example, metals such as silicon, copper, chromium, iron, and aluminum, substrates made of inorganic materials such as glass, titanium oxide, silica, and mica, substrates made of organic compounds such as acrylic plates, polystyrene, cellulose, cellulose acetate, and phenol resins Is mentioned.
Moreover, the magnitude | size and shape of the board | substrate used in this aspect are not specifically limited. The substrate does not necessarily have a smooth surface, and substrates of various materials and shapes can be selected as appropriate. For example, a substrate having a curved surface, a flat plate having an uneven surface, and a substrate having various shapes such as a flake shape can be used.
An inorganic and / or organic film may be provided on the substrate surface. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC).

Before forming the photosensitive resin film 2 on the substrate, the substrate surface may be washed. In some cases, the neutralization film 3 can be formed satisfactorily by cleaning the substrate surface.
As a cleaning method, a conventionally known method can be used, and examples thereof include oxygen plasma treatment, hydrogen plasma treatment, ozone oxidation treatment, acid-alkali treatment, and chemical modification treatment. As an example, there is a method in which a substrate is immersed in an acid solution such as sulfuric acid / hydrogen peroxide aqueous solution, then washed with water and dried.

The wavelength used for the exposure is not particularly limited, and ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. Can be done using radiation.

The exposure method of the photosensitive resin film 2 may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be immersion exposure (Liquid Immersion Lithography).
In immersion exposure, the space between the photosensitive resin film 2 and the lens at the lowest position of the exposure apparatus is filled with a solvent (immersion medium) having a refractive index larger than that of air in advance, and exposure (immersion exposure) is performed in that state. Is an exposure method.
As the immersion medium, a solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the exposed photosensitive resin film 2 is preferable. The refractive index of such a solvent is not particularly limited as long as it is within the above range.
Examples of the solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the photosensitive resin film 2 include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent. It is done.
Specific examples of the fluorine-based inert liquid include a fluorine-based compound such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F ₇ as a main component. Examples thereof include liquids, and those having a boiling point of 70 to 180 ° C are preferable, and those having a boiling point of 80 to 160 ° C are more preferable. It is preferable that the fluorine-based inert liquid has a boiling point in the above range since the medium used for immersion can be removed by a simple method after the exposure is completed.
As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.
More specifically, examples of the perfluoroalkyl ether compound include perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ° C.). Examples of the perfluoroalkylamine compound include perfluorotributylamine ( Boiling point of 174 ° C.).
As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility, and the like.

The organic solvent contained in the organic developer is not particularly limited as long as it can dissolve the photosensitive resin before exposure, and can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
A known additive can be blended in the organic developer as required. Examples of the additive include a surfactant. The surfactant is not particularly limited. For example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
When the surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0. 0% with respect to the total amount of the organic developer. 5 mass% is more preferable.

  The negative development can be carried out by a known development method. For example, a method in which the support 1 is immersed in a developer for a predetermined time (dip method), and the developer is raised on the surface of the support 1 by surface tension. A method of standing still for a certain time (paddle method), a method of spraying a developer on the surface of the support 1 (spray method), and developing while scanning the developer coating nozzle at a constant speed on a support rotating at a constant speed. Examples thereof include a method of continuously applying the liquid (dynamic dispensing method).

  The rinse treatment (washing treatment) using the rinse liquid can be performed by a known rinse method. As the method, for example, a method of continuously applying the rinse liquid onto the support 1 rotating at a constant speed (rotary coating method), a method of immersing the support 1 in the rinse liquid for a predetermined time (dip method), a support The method (spray method) etc. which spray the rinse liquid on the body 1 surface are mentioned.

  The photosensitive resin composition for forming a pre-pattern is one that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid, and is generally used for forming a photosensitive resin film. It can be used by appropriately selecting from the photosensitive resin composition or its modified product. When the photosensitive resin composition used in this embodiment is a photosensitive resin film, the higher the resistance to solvents, the heat resistance, and the solubility in an alkali developer are preferred. The detail about this photosensitive resin composition is mentioned later.

<Step (2)>
In the step (2), a neutralized film containing a surface treatment agent is formed on the support on which the prepattern is formed in the step (1) (the support on which the prepattern is formed is neutralized). To do).
The neutralization treatment refers to a treatment for modifying the support surface so as to have affinity for any block constituting the block copolymer. By performing a neutralization process, it can suppress that only the phase which consists of a specific block by phase separation contacts a support body surface. Considering this point, in order to form a phase separation structure on the support surface by phase separation, before forming the layer containing the block copolymer, a neutralized film corresponding to the type of block copolymer to be used is formed on the support surface. Form it. Specifically, a thin film (neutralized film) containing a surface treatment agent having affinity with any block constituting the block copolymer is formed on the support surface.

The neutralization film 3 can be formed, for example, by applying a surface treatment agent on the support 1 on which a pre-pattern is formed.
Specifically, a surface treatment agent is applied onto the support 1 on which the prepattern is formed by spin coating or the like so as to cover the prepattern. Thereafter, baking is preferably performed at a temperature of 160 to 270 ° C., more preferably 180 to 250 ° C., preferably for 30 to 600 seconds, more preferably for 60 to 450 seconds to form the neutralized film 3. .
The thickness of the neutralization film 3 may be any thickness that can cause phase separation, and is preferably 2 nm or more, and more preferably 5 to 15 nm.
The surface treating agent is preferably applied on the support 1 on which the prepattern is formed so as to cover the prepattern. Thereby, the space portion of the pre-pattern, that is, the exposed portion 1s of the support 1 can be sufficiently covered, and the pattern made of the neutralized film 3a can be formed better.

(Surface treatment agent)
As the surface treatment agent, a resin composition can be used.
Such a resin composition can be appropriately selected from conventionally known resin compositions used for thin film formation according to the type of block constituting the block copolymer.
The resin composition used as the surface treatment agent may be a heat-polymerizable resin composition or a photosensitive resin composition such as a positive resist composition or a negative resist composition. In addition, a non-polymerizable film formed by applying a compound as a surface treating agent and applying the compound may be used as a neutralized film. For example, a siloxane-based organic monomolecular film formed using phenethyltrichlorosilane, octadecyltrichlorosilane, hexamethyldisilazane, or the like as a surface treatment agent can also be suitably used as the neutralization film 3.

Examples of such a surface treatment agent include a resin composition containing a resin having all the constituent units of each block constituting the block copolymer, and a constituent unit having high affinity with each block constituting the block copolymer. In addition, a resin composition containing a resin that also has a resin may be used.
For example, in the case of using a block copolymer (PS-b-PMMA) of a block composed of a repeating unit of styrene and a block composed of a repeating unit of methyl methacrylate (PS-b-PMMA), styrene and methyl methacrylate are used as the surface treatment agent. Including both a composition containing a resin having both as a structural unit, a site having a high affinity for styrene such as an aromatic ring, and a site having a high affinity for methyl methacrylate (such as a highly polar functional group) It is preferred to use a compound or composition.
Examples of resins having both styrene and methyl methacrylate as structural units include random copolymers of styrene and methyl methacrylate, and alternating polymers of styrene and methyl methacrylate (in which each monomer is copolymerized alternately) ) And the like.
In addition, as a composition including both a site having a high affinity for styrene and a site having a high affinity for methyl methacrylate, for example, as a monomer, at least a monomer having an aromatic ring, and a functional group having a high polarity And a composition containing a resin obtained by polymerizing a monomer having a. As a monomer having an aromatic ring, one hydrogen atom is removed from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group. And a monomer having a heteroaryl group in which part of the carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. In addition, as a monomer having a highly polar functional group, a part of hydrogen atoms of a trimethoxysilyl group, a trichlorosilyl group, an epoxy group, a glycidyl group, a carboxy group, a hydroxyl group, a cyano group, and an alkyl group are substituted with a hydroxy group. And monomers having a hydroxyalkyl group or the like.
In addition, as a compound containing both a site having a high affinity for styrene and a site having a high affinity for methyl methacrylate, a compound containing both an aryl group such as phenethyltrichlorosilane and a functional group having a high polarity And compounds containing both an alkyl group such as an alkylsilane compound and a highly polar functional group.

The resin composition used as the surface treatment agent can be produced by dissolving the aforementioned resin in a solvent.
Such a solvent is not particularly limited as long as it can dissolve each component to be used to form a uniform solution. For example, lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, Ketones such as methyl isopentyl ketone and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol mono Compounds having an ester bond such as acetate, monomethyl ether, monoethyl ether, monopropyl of the polyhydric alcohols or the compound having an ester bond -Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ether or monophenyl ether such as ether and monobutyl ether [in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) Preferred]; cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc. Esters: anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, ethyl benzene, diethyl benzene, pen Aromatic organic solvents such as tilbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene and the like can be mentioned.
These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Of these, PGMEA, PGME, cyclohexanone, and EL are preferable.

Moreover, the mixed solvent which mixed PGMEA and the polar solvent is also preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, and is preferably in the range of 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be inside. For example, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7: 3. When PGME and cyclohexanone are blended as polar solvents, the mass ratio of PGMEA: (PGME + cyclohexanone) is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and still more preferably 3. : 7 to 7: 3.
In addition, as the organic solvent in the block copolymer solution, PGMEA, EL, or a mixed solvent of PGMEA and a polar solvent and a mixed solvent of γ-butyrolactone are also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.

<Step (3)>
In the step (3), the prepattern and the neutralized film formed on the support in the step (2) are developed with alkali, and the prepattern is removed from the support. Thereby, the pattern (guide pattern) which consists of this neutralization film | membrane is formed on this support body.
In this embodiment, the photosensitive resin film 2a constituting the pre-pattern is formed by negative development using an organic developer using a photosensitive resin composition whose solubility in a developer is changed by the action of an acid. The formed photosensitive resin film 2a is soluble in an alkaline developer. Therefore, by neutral development, the photosensitive resin film 2a is dissolved in the alkaline developer, the prepattern is removed from the support 1, and the neutral formed in the space portion of the prepattern (the exposed portion 1s of the support 1). Only the chemical film 3 a remains on the support 1.
The pre-pattern is removed by alkali development, and the pre-pattern is present on the surface opposite to the support 1 side (pre-pattern upper surface) and on the side surface in the vicinity of the opposite surface (pre-pattern side surface). The neutralized film 3 that has been removed is also removed.

Examples of the alkaline developer include 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. The alkali development can be carried out by a known development method, and can be carried out in the same manner as the development method in the negative development described above.
After the alkali development, a rinse treatment is preferably performed. The rinse treatment is preferably a rinse treatment using pure water. The rinsing process can be performed by a known rinsing method, and can be performed in the same manner as in the negative development described above.
Drying is performed after alkali development or rinsing. In some cases, baking treatment (post-baking) may be performed after alkali development. The baking (post-baking) is preferably performed at 90 ° C. or higher, more preferably performed at 100 ° C. or higher, and particularly preferably performed at 100 to 130 ° C. The heating time is preferably 30 to 100 seconds, more preferably 60 to 80 seconds.

  The pattern formation method of this aspect is not restricted to embodiment mentioned above, In addition to process (1)-(3), the other process may be included.

(Photosensitive resin composition)
In the pattern forming method of this embodiment, a photosensitive resin composition is used that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid.
Examples of the photosensitive resin composition include those containing a substrate component (A) (hereinafter also referred to as “component (A)”) whose solubility in a developing solution is changed by the action of an acid.
When a photosensitive resin film is formed using such a photosensitive resin composition and selective exposure is performed on the photosensitive resin film, an acid is generated in the exposed portion, and the action of the acid causes the component (A). While the solubility in the developer changes, the solubility of the component (A) in the developer does not change in the unexposed area, so a difference in solubility in the developer occurs between the exposed area and the unexposed area. Therefore, when the photosensitive resin film is developed, when the photosensitive resin composition is a positive type, the exposed portion is dissolved and removed to form a positive type photosensitive resin pattern (pre-pattern), and the photosensitive resin composition When the object is a negative type, the unexposed part is dissolved and removed to form a negative type photosensitive resin pattern (pre-pattern).
In the present specification, a photosensitive resin composition in which an exposed portion is dissolved and removed to form a positive photosensitive resin pattern is referred to as a positive photosensitive resin composition, and an unexposed portion is dissolved and removed to obtain a negative photosensitive resin composition. The photosensitive resin composition that forms the resin pattern is referred to as a negative photosensitive resin composition.
The photosensitive resin composition used in this embodiment may be a positive photosensitive resin composition or a negative photosensitive resin composition.
Further, the photosensitive resin composition used in this embodiment may be used for an alkali development process using an alkali developer for the development process, and a developer (organic developer) containing an organic solvent is used for the development process. It may be for a solvent development process.
Among such photosensitive resin compositions, in the pattern forming method of this embodiment, in step (1), a negative photosensitive resin pattern (pre-pattern) is formed by negative development, and in step (3), A material suitable for dissolving and removing the photosensitive resin pattern by alkali development is employed.

The photosensitive resin composition used in this embodiment has an acid generating ability to generate an acid upon exposure, and the component (A) may generate an acid upon exposure, and is blended separately from the component (A). The added additive component may generate an acid upon exposure.
Specifically, the photosensitive resin composition may contain (1) an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as “component (B)”); (2) The component (A) may be a component that generates an acid upon exposure; (3) The component (A) is a component that generates an acid upon exposure, and further contains a component (B). It may be.
That is, in the case of the above (2) and (3), the component (A) is a “base material component that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid”. When the component (A) is a base material component that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid, the component (A1) described later generates an acid upon exposure, and A polymer compound whose solubility in a developing solution is changed by the action of an acid is preferable. As such a polymer compound, a polymer compound having a structural unit that generates an acid upon exposure can be used. A well-known thing can be used as a structural unit which generate | occur | produces an acid by exposure.
The photosensitive resin composition used in this embodiment is preferably the above (1).

-(A) component In this invention, a "base-material component" is an organic compound which has film forming ability, Preferably the organic compound whose molecular weight is 500 or more is used. When the molecular weight of the organic compound is 500 or more, the film forming ability is improved, and in addition, a nano-level photosensitive resin pattern is easily formed.
Organic compounds used as the base material component are roughly classified into non-polymers and polymers.
As the non-polymer, those having a molecular weight of 500 or more and less than 4000 are usually used. Hereinafter, the “low molecular compound” refers to a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, those having a molecular weight of 1000 or more are usually used. Hereinafter, the term “resin” or “polymer compound” refers to a polymer having a molecular weight of 1000 or more.
As the molecular weight of the polymer, a polystyrene-reduced mass average molecular weight by GPC (gel permeation chromatography) is used.

The component (A) used in this embodiment may be one that increases the solubility in the developer by the action of an acid, or may decrease the solubility in the developer by the action of an acid. Among these, the component (A) is preferably a base material component whose solubility in an organic solvent is reduced by the action of an acid. In addition, the component (A) is preferably a base material component whose solubility in an alkaline developer is increased by the action of an acid.
In this embodiment, in particular, as the component (A), the polymer compound (A1) having a structural unit (a1) containing an acid-decomposable group whose polarity is increased by the action of an acid (hereinafter referred to as “(A1) ) Component ") is preferred.
The photosensitive resin composition containing the component (A1) generates an acid upon exposure, and the exposed part of the component (A1) becomes highly polar. Due to the action of the acid, the component (A1) is dissolved in an organic solvent. Sex is reduced. Therefore, in the pre-pattern formation, when selective exposure is performed on the photosensitive resin film obtained using the photosensitive resin composition, a developer containing an organic solvent in the exposed portion of the photosensitive resin film ( While the solubility in the organic developer is reduced, the solubility in the organic developer in the unexposed area does not change, and development using the organic developer removes the unexposed area. A pre-pattern is formed.
Since the exposed portion (prepattern) in the photosensitive resin film has reduced solubility in organic solvents (improves resistance to the solvent), a neutralized film is formed on the prepattern in step (2). At this time, the prepattern is hardly affected by the solvent contained in the surface treatment agent for forming the neutralized film.
Moreover, since the exposure part in this photosensitive resin film has high polarity, it is easy to melt | dissolve in an alkali developing solution. Therefore, the prepattern (the exposed portion in the photosensitive resin film) is dissolved and removed by alkali development.
As the component (A), it is preferable to use at least the component (A1), and other high molecular compounds and / or low molecular compounds may be used in combination with the component (A1).
The proportion of the component (A1) in the component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, further preferably 75% by mass or more, and 100% by mass with respect to the total mass of the component (A). It may be. If the proportion is 25% by mass or more, a photosensitive resin pattern having good lithography characteristics and shape can be easily obtained.

-(A1) component A (A1) component is a high molecular compound which has the structural unit (a1) containing the acid-decomposable group which polarity increases by the effect | action of an acid.
Among these, the component (A1) is particularly preferably a polymer compound having a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent.

... Structural unit (a1)
The structural unit (a1) is a structural unit containing an acid-decomposable group whose polarity is increased by the action of an acid.
The “acid-decomposable group” is an acid-decomposable group that can cleave at least part of bonds in the structure of the acid-decomposable group by the action of an acid.
Examples of the acid-decomposable group whose polarity increases by the action of an acid include a group that decomposes by the action of an acid to generate a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, a sulfo group (—SO ₃ H), and the like. Among these, a polar group containing —OH in the structure (hereinafter sometimes referred to as “OH-containing polar group”) is preferable, a carboxy group or a hydroxyl group is more preferable, and a carboxy group is particularly preferable.
More specifically, examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
Here, the “acid-dissociable group” means (i) a group having acid-dissociable properties capable of cleaving a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group by the action of an acid, Alternatively, (ii) after a partial bond is cleaved by the action of an acid, a further decarboxylation reaction occurs, whereby a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group is cleaved. Both of the resulting groups.
The acid-dissociable group constituting the acid-decomposable group must be a group having a lower polarity than the polar group generated by dissociation of the acid-dissociable group. Is dissociated, a polar group having a polarity higher than that of the acid dissociable group is generated to increase the polarity. As a result, the polarity of the entire component (A1) increases. As the polarity increases, the solubility in the developer changes relatively, the solubility decreases when the developer is an organic developer, and the solubility decreases when the developer is an alkaline developer. Increase.

The acid-dissociable group is not particularly limited, and those that have been proposed as acid-dissociable groups for base resins for chemically amplified resists can be used.
Examples of the acid dissociable group that protects a carboxy group or a hydroxyl group among the polar groups include, for example, an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter referred to as “acetal acid dissociable group”). May be included).

［式中、Ｒａ’^１、Ｒａ’^２は水素原子またはアルキル基であり、Ｒａ’^３は炭化水素基であって、Ｒａ’^３は、Ｒａ’^１、Ｒａ’^２のいずれかと結合して環を形成してもよい。］

[Wherein, Ra ′ ¹ and Ra ′ ² are a hydrogen atom or an alkyl group, Ra ′ ³ is a hydrocarbon group, and Ra ′ ³ is bonded to either Ra ′ ¹ or Ra ′ ² to form a ring. May be formed. ]

In formula (a1-r-1), at least one of Ra ′ ¹ and Ra ′ ² is preferably a hydrogen atom, and more preferably both are hydrogen atoms.
In the case where Ra ′ ¹ or Ra ′ ² is an alkyl group, the alkyl group is the alkyl group mentioned as the substituent that may be bonded to the α-position carbon atom in the description of the α-substituted acrylate ester. The same thing is mentioned, A C1-C5 alkyl group is preferable. Specifically, a linear or branched alkyl group is preferable. More specifically, 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, a neopentyl group, and the like can be given. More preferred is a methyl group.

In formula (a1-r-1), examples of the Ra ′ ³ hydrocarbon group 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 still more preferably 1 or 2. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

  The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, and the like is preferably isopropyl group.

When Ra ′ ³ 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 alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom 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 obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically, Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When the cyclic hydrocarbon group of Ra ′ ³ is an aromatic hydrocarbon group, the aromatic ring contained is specifically an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene; the aromatic hydrocarbon ring An aromatic heterocyclic ring in which a part of the carbon atoms constituting is substituted with a heteroatom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group); an aromatic compound containing two or more aromatic rings A group obtained by removing one hydrogen atom from (for example, biphenyl, fluorene, etc.); 1 of the hydrogen atoms of a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring Groups substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group) and the like. .
The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

When Ra ′ ³ is bonded to either Ra ′ ¹ or Ra ′ ² to form a ring, the cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

  Moreover, as an acid dissociable group which protects a carboxy group among the said polar groups, the acid dissociable group represented by the following general formula (a1-r-2) is mentioned suitably, for example.

［式中、Ｒａ’^４〜Ｒａ’^６はそれぞれ置換基を有していてもよい炭化水素基であって、Ｒａ’^５とＲａ’^６とは互いに結合して環を形成してもよい。］

[Wherein, Ra ′ ^{4 to} Ra ′ ⁶ are each a hydrocarbon group which may have a substituent, and Ra ′ ⁵ and Ra ′ ⁶ may be bonded to each other to form a ring. ]

In the formula (a1-r-2), examples of the hydrocarbon group represented by Ra ′ ^{4 to} Ra ′ ⁶ include the same groups as those described above for Ra ′ ³ .
The hydrocarbon group in Ra ′ ^{4 to} Ra ′ ⁶ may have a substituent.
“The hydrocarbon group may have a substituent” means that part or all of the hydrogen atoms in the hydrocarbon group may be substituted with a substituent.
R ² has 4 to 20 carbon atoms, and this 4 to 20 carbon atoms includes a carbon atom in the substituent.
As the substituent here, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc .; preferably a fluorine atom), a halogenated alkyl group (preferably a fluorinated alkyl group), an oxygen atom (═O), cyano group _{(-CN), - CO 2 OCH} 3, -NO 2 , and the like. Specifically, as the halogenated alkyl group, part or all of the hydrogen atoms of the “alkyl group (preferably an alkyl group having 1 to 5 carbon atoms)” are halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) Group preferably substituted with a fluorine atom).
However, in the hydrocarbon group in Ra ′ ^{4 to} Ra ′ ⁶ , a part of the carbon atoms constituting the hydrocarbon group may be substituted with atoms or atomic groups other than carbon atoms. Examples of atoms other than carbon atoms include heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms.

In the formula (a1-r-2), Ra ′ ⁴ is preferably an alkyl group having 1 to 5 carbon atoms out of Ra ′ ^{4 to} Ra ′ ⁶ .
When Ra ′ ⁵ and Ra ′ ⁶ are bonded to each other to form a ring, for example, a group represented by the following general formula (a1-r2-1) can be mentioned.
On the other hand, when Ra ′ ^{4 to} Ra ′ ⁶ are not bonded to each other and each is an independent hydrocarbon group, a group represented by the following general formula (a1-r2-2) is exemplified.

［式中、Ｒａ’^１０は炭素数１〜１０のアルキル基である。Ｒａ’^１１はＲａ’^１０が結合した炭素原子と共に脂肪族環式基を形成する基である。Ｒａ’^１２〜Ｒａ’^１４は、それぞれ独立に炭化水素基を示す。］

[In the formula, Ra ′ ¹⁰ is an alkyl group having 1 to ¹⁰ carbon atoms. Ra ′ ¹¹ is a group that forms an aliphatic cyclic group together with the carbon atom to which Ra ′ ¹⁰ is bonded. Ra ′ ^{12 to} Ra ′ ¹⁴ each independently represent a hydrocarbon group. ]

In the formula (a1-r2-1), the alkyl group having 1 to ¹⁰ carbon atoms in Ra ′ ¹⁰ is a linear or branched alkyl group of Ra ′ ³ in the formula (a1-r-1). The groups mentioned are preferred. In formula (a1-r2-1), Ra ′ ^{11 and} the aliphatic cyclic group formed together with the carbon atom to which Ra ′ ¹⁰ is bonded are the cyclic hydrocarbon of Ra ′ ³ in formula (a1-r-1) The groups listed as groups are preferred, and monocyclic alicyclic hydrocarbon groups are more preferred.

In the formula (a1-r2-2), Ra ′ ¹² and Ra ′ ¹⁴ are preferably each independently an alkyl group having 1 to 10 carbon atoms, and the alkyl group may be represented by the formula (a1-r-1). ) Is more preferably a group exemplified as a linear or branched alkyl group of Ra ′ ³ , more preferably a linear alkyl group having 1 to 5 carbon atoms, and a methyl group or an ethyl group. Is particularly preferred.
In formula (a1-r2-2), Ra ′ ¹³ represents a linear or branched alkyl group exemplified as the hydrocarbon group for Ra ′ ³ in formula (a1-r-1), or a single group. A cyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group is preferable. Among these, Ra ′ ¹³ is more preferably a group exemplified as a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group.

  Specific examples of the group represented by the formula (a1-r2-1) are given below. In addition, in this specification, * mark in a formula shows a bond (bonding position with oxygen atom -O-).

  Specific examples of the group represented by the formula (a1-r2-2) are given below.

  Among the polar groups, examples of the acid dissociable group for protecting the hydroxyl group include an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter referred to as “tertiary alkyloxycarbonyl acid” for the sake of convenience). Sometimes referred to as a “dissociable group”).

［式中、Ｒａ’^７〜Ｒａ’^９はそれぞれアルキル基である。］

[Wherein, Ra ′ ^{7 to} Ra ′ ⁹ each represents an alkyl group. ]

In formula (a1-r-3), Ra ′ ^{7 to} Ra ′ ⁹ are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably 1 to 3 groups.
Moreover, it is preferable that the total carbon number of each alkyl group is 3-7, it is more preferable that it is 3-5, and it is most preferable that it is 3-4.

  The structural unit (a1) is a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, and an acid whose polarity is increased by the action of an acid. Structural unit containing a decomposable group; a structural unit derived from acrylamide and containing an acid-decomposable group whose polarity is increased by the action of an acid; a hydroxyl group of a structural unit derived from hydroxystyrene or a hydroxystyrene derivative A structural unit in which at least a part of the hydrogen atoms in is protected by a substituent containing the acid-decomposable group; a hydrogen atom in —C (═O) —OH of a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative And a structural unit in which at least a part of the group is protected by a substituent containing the acid-decomposable group.

Among the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
Preferable specific examples of the structural unit (a1) include structural units represented by the following general formula (a1-1) or (a1-2).

［式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｖａ^１はエーテル結合を有していてもよい２価の炭化水素基であり、ｎ_ａ１は０〜２であり、Ｒａ^１は上記式（ａ１−ｒ−１）又は（ａ１−ｒ−２）で表される酸解離性基である。Ｗａ^１はｎ_ａ２＋１価の炭化水素基であり、ｎ_ａ２は１〜３であり、Ｒａ^２は上記式（ａ１−ｒ−１）又は（ａ１−ｒ−３）で表される酸解離性基である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Va ¹ is a divalent hydrocarbon group which may have an ether bond, n _a1 is 0 to 2, and Ra ¹ is the above formula (a1-r-1) or (a1-r-2) It is an acid dissociable group represented by. Wa ¹ is a n _a2 +1 valent hydrocarbon group, n _a2 is 1 to 3, and Ra ² is an acid dissociation property represented by the above formula (a1-r-1) or (a1-r-3). It is a group. ]

In the formula (a1-1), the alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically a methyl group or an ethyl group. Propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
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 is most preferably a hydrogen atom or a methyl group in terms of industrial availability.

The hydrocarbon group for Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group as a divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is usually preferably saturated.
More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, and the like.
Further, Va ¹ may have an ether bond (—O—) between carbon atoms of the divalent hydrocarbon group. One or two or more ether bonds may be present in Va ¹ .

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include 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 obtained by removing two hydrogen atoms 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 obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, and 6 to 6 carbon atoms. 15 is particularly preferable, and 6 to 10 is most preferable. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; some of the carbon atoms constituting the aromatic hydrocarbon ring are heterogeneous. Aromatic heterocycles substituted with atoms. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) A group in which one of the hydrogen atoms is substituted with an alkylene group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) And a group obtained by further removing one hydrogen atom from the aryl group. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In the formula (a1-2), the n _a2 +1 valent hydrocarbon group in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group including a ring in the structure, or a linear or branched aliphatic hydrocarbon group. Examples thereof include a combination of an aliphatic hydrocarbon group containing a ring in the structure.
The n _a2 +1 valence is preferably 2 to 4, and more preferably 2 or 3.

Specific examples of the structural unit represented by the formula (a1-1) are shown below. In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

  Specific examples of the structural unit represented by the formula (a1-2) are shown below.

As the structural unit (a1) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
The proportion of the structural unit (a1) in the component (A1) is preferably from 10 to 80 mol%, more preferably from 15 to 75 mol%, more preferably from 20 to 70 mol%, based on all structural units constituting the component (A1). Is more preferable.
By setting the ratio of the structural unit (a1) to the lower limit value or more, a photosensitive resin pattern (pre-pattern) can be easily obtained, and lithography properties such as sensitivity, resolution, and LWR are also improved. In addition, by setting the upper limit value or less, it is possible to balance with other structural units.

... Other structural unit (A1) A component may further have another structural unit which does not correspond to the structural unit (a1) mentioned above.
The other structural unit is not particularly limited as long as it is a structural unit that is not classified into the above-mentioned structural units. For resist resins for ArF excimer laser, KrF excimer laser (preferably for ArF excimer laser), etc. Many things conventionally known can be used as what is used, for example, the structural units (a2)-(a4) shown below etc. are mentioned.

Structural unit (a2):
In addition to the structural unit (a1), the component (A1) preferably has a structural unit (a2) containing a lactone-containing cyclic group, an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group.
The lactone-containing cyclic group, -SO ₂ -containing cyclic group or carbonate-containing cyclic group of the structural unit (a2) is used to increase the adhesion of the photosensitive resin film to the support when forming a prepattern. It is effective. In addition, the resulting photosensitive resin film contributes to improvement of solvent resistance, heat resistance, and solubility in an alkali developer.
When the neutralized film 3 is formed on the prepattern in step (2) due to the increased resistance to the solvent, the prepattern is affected by the solvent contained in the surface treatment agent for forming the neutralized film. It becomes difficult.
Further, since the heat resistance is increased, the pattern is hardly deformed when the pre-pattern is baked at a high temperature. Thereby, after negative development, baking can be performed at a high temperature (preferably 180 ° C. or higher), and resistance to a solvent can be easily imparted to the prepattern.
Furthermore, the pre-pattern can be easily removed in the step (3) by increasing the solubility in an alkali developer.

The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing —O—C (═O) — in the ring skeleton. The lactone ring is counted as the first ring. When only the lactone ring is present, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
The lactone-containing cyclic group in the structural unit (a2) is not particularly limited, and any lactone-containing cyclic group can be used. Specific examples include groups represented by general formulas (a2-r-1) to (a2-r-7) shown below.

［式中、Ｒａ’^２１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子（−Ｏ−）もしくは硫黄原子（−Ｓ−）を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｎ’は０〜２の整数であり、ｍ’は０または１である。］

[Wherein, Ra ′ ²¹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom, alkyl group, lactone-containing cyclic group, carbonate-containing cyclic group, or —SO ₂ -containing cyclic group; A ″ is an oxygen atom (—O—) or a sulfur atom (— S—) may be an alkylene group having 1 to 5 carbon atoms, an oxygen atom or a sulfur atom, n ′ is an integer of 0 to 2, and m ′ is 0 or 1. ]

In the general formula (a2-r-1) ~ (a2-r-7), the alkyl group in Ra ^'21, preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples 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, a neopentyl group, and a hexyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
The alkoxy group in the ra ^'21, preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, groups of the the Ra 'group and an oxygen atom mentioned as the alkyl group in ²¹ (-O-) are linked and the like.
Examples of the halogen atom in Ra ′ ²¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
'Examples of the halogenated alkyl group for ^21, the Ra' Ra part or all of the hydrogen atoms of the alkyl group in ²¹ can be mentioned it has been substituted with the aforementioned halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

In —COOR ″ and —OC (═O) R ″ in Ra ′ ²¹ , R ″ is any hydrogen atom, alkyl group, lactone-containing cyclic group, carbonate-containing cyclic group, or —SO ₂ -containing cyclic group. It is.
The alkyl group for R ″ may be linear, branched or cyclic, and preferably has 1 to 15 carbon atoms.
When R ″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. preferable.
When R ″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a fluorine atom Alternatively, one or more hydrogen atoms are removed from a polycycloalkane such as a monocycloalkane, bicycloalkane, tricycloalkane, or tetracycloalkane, which may or may not be substituted with a fluorinated alkyl group. More specifically, one or more hydrogen atoms are removed from a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Group.
Examples of the lactone-containing cyclic group for R ″ include the same groups as those represented by general formulas (a2-r-1) to (a2-r-7).
The carbonate-containing cyclic group for R ″ is the same as the carbonate-containing cyclic group described later, and specifically, groups represented by general formulas (ax3-r-1) to (ax3-r-3), respectively. Is mentioned.
The —SO ₂ — containing cyclic group in R ″ is the same as the later-described —SO ₂ — containing cyclic group, and specifically, is represented by the general formulas (a5-r-1) to (a5-r-4) And groups represented respectively by
The hydroxyalkyl group in Ra ′ ²¹ is preferably one having 1 to 6 carbon atoms, and specifically, a group in which at least one hydrogen atom of the alkyl group in Ra ′ ²¹ is substituted with a hydroxyl group can be mentioned. .

In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A ″ is linear or branched. An alkylene group is preferable, and examples include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, etc. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include the terminal of the alkylene group or carbon. between atoms -O- or -S- can be mentioned a group intervening, for _{example, -O-CH 2 -, -} CH 2 -O-CH 2 -, - S-CH 2 -, - CH 2 -S- CH ₂ -, etc. as .A "which include an alkylene group, or -O- is preferable of 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

  Specific examples of groups represented by general formulas (a2-r-1) to (a2-r-7) are given below.

The “—SO ₂ -containing cyclic group” refers to a cyclic group containing a ring containing —SO ₂ — in the ring skeleton, specifically, the sulfur atom (S) in —SO ₂ — is It is a cyclic group that forms part of the ring skeleton of the cyclic group. The ring containing —SO ₂ — in the ring skeleton is counted as the first ring, and when it is only the ring, it is a monocyclic group, and when it has another ring structure, it is a polycyclic group regardless of the structure. Called. The —SO ₂ — containing cyclic group may be a monocyclic group or a polycyclic group.
-SO ₂ - containing cyclic group, in particular, -O-SO ₂ - within the ring skeleton cyclic group containing, i.e. -O-SO ₂ - -O-S- medium is a part of the ring skeleton A cyclic group containing a sultone ring to be formed is preferable.
More specifically, examples of the —SO ₂ -containing cyclic group include groups represented by general formulas (a5-r-1) to (a5-r-4) shown below.

［式中、Ｒａ’^５１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｎ’は０〜２の整数である。］

[Wherein, Ra ′ ⁵¹ independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom, alkyl group, lactone-containing cyclic group, carbonate-containing cyclic group, or —SO ₂ -containing cyclic group; A ″ is a carbon that may contain an oxygen atom or a sulfur atom It is a C 1-5 alkylene group, an oxygen atom or a sulfur atom, and n ′ is an integer of 0-2. ]

In general formulas (a5-r-1) to (a5-r-4), A ″ represents the general formulas (a2-r-2), (a2-r-3), and (a2-r-5). Same as A ″ in the middle.
As the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR ″, —OC (═O) R ″, and hydroxyalkyl group in Ra ′ ⁵¹ , the above general formulas (a2-r-1) to ( a2-r-7) as in the same as those exemplified in the description of the Ra ^'21 of the like.
Specific examples of groups represented by general formulas (a5-r-1) to (a5-r-4) are given below. “Ac” in the formula represents an acetyl group.

The “carbonate-containing cyclic group” refers to a cyclic group containing a ring (carbonate ring) containing —O—C (═O) —O— in the ring skeleton. When the carbonate ring is counted as the first ring, the carbonate ring alone is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.
Any carbonate ring-containing cyclic group can be used without any particular limitation. Specific examples include groups represented by the following general formulas (ax3-r-1) to (ax3-r-3).

［式中、Ｒａ’^ｘ３１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｐ’は０〜３の整数であり、ｑ’は０または１である。］

[ ^Wherein , Ra ′ ^x31 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom, alkyl group, lactone-containing cyclic group, carbonate-containing cyclic group, or —SO ₂ -containing cyclic group; A ″ is a carbon that may contain an oxygen atom or a sulfur atom It is an alkylene group of formulas 1 to 5, an oxygen atom or a sulfur atom, p ′ is an integer of 0 to 3, and q ′ is 0 or 1. ]

In the general formulas (ax3-r-1) to (ax3-r-3), A ″ represents the general formulas (a2-r-2), (a2-r-3), (a2-r-5). Same as A ″ in the middle.
As the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR ″, —OC (═O) R ″, and hydroxyalkyl group in Ra ′ ³¹ , the above general formulas (a2-r-1) to ( a2-r-7) as in the same as those exemplified in the description of the Ra ^'21 of the like.
Specific examples of groups represented by general formulas (ax3-r-1) to (ax3-r-3) are given below.

As the structural unit (a2), a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent is preferable.
The structural unit (a2) is preferably a structural unit represented by the following general formula (a2-1).

［式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｙａ^２１は単結合または２価の連結基である。Ｌａ^２１は−Ｏ−、−ＣＯＯ−、−ＣＯＮ（Ｒ’）−、−ＯＣＯ−、−ＣＯＮＨＣＯ−又は−ＣＯＮＨＣＳ−であり、Ｒ’は水素原子またはメチル基を示す。ただしＬａ^２１が−Ｏ−の場合、Ｙａ^２１は−ＣＯ−にはならない。Ｒａ^２１はラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ²¹ is a single bond or a divalent linking group. La ²¹ represents —O—, —COO—, —CON (R ′) —, —OCO—, —CONHCO— or —CONHCS—, and R ′ represents a hydrogen atom or a methyl group. However, when La ²¹ is —O—, Ya ²¹ is not —CO—. Ra ²¹ is a lactone-containing cyclic group, a carbonate-containing cyclic group, or an —SO ₂ -containing cyclic group. ]

In formula (a2-1), R is the same as described above.
The divalent linking group of Ya ²¹ is not particularly limited, and preferred examples thereof include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

When Ya ²¹ is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and 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 the structure, and the like.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (excluding two hydrogen atoms from the aliphatic hydrocarbon ring) Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group is a linear or branched chain fatty acid. Group intervening in the middle of the group hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms 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 obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and 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, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group. Most preferred is 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, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.
In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing the hetero atom, —O—, —C (═O) —O—, —S—, —S (═O) ₂ —, and —S (═O) ₂ —O— are preferable.

The aromatic hydrocarbon group as a divalent 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. It is preferable that carbon number of an aromatic ring is 5-30, 5-20 are more preferable, 6-15 are more preferable, and 6-12 are especially preferable. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms, and the like. Can be mentioned. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings A group obtained by removing two hydrogen atoms from (for example, biphenyl, fluorene, etc.); 1 of the hydrogen atoms of a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring A group substituted with an alkylene group (for example, an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) A group in which one atom is further removed). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In the aromatic 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, the halogen atom and the halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

When Ya ²¹ is a divalent linking group containing a hetero atom, preferred examples of the linking group include —O—, —C (═O) —O—, —C (═O) —, and —O—C. (═O) —O—, —C (═O) —NH—, —NH—, —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-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 - C (═O) —O—, —C (═O) —O—Y ²¹ —, — [Y ²¹ —C (═O) —O] _{m ″} —Y ²² —, —Y ²¹ —O—C ( Group represented by ═O) —Y ²² — or —Y ²¹ —S (═O) ₂ —O—Y ²² —, wherein Y ²¹ and Y ²² each independently have a substituent. A divalent hydrocarbon group, It is an oxygen atom, m "is an integer of 0 to 3. ] Etc. are mentioned.
The divalent linking group containing a hetero atom is -C (= O) -NH-, -C (= O) -NH-C (= O)-, -NH-, -NH-C (= NH). In the case of-, the H may be substituted with a substituent such as an alkyl group or acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21 -, - [Y 21 - C (═O) —O] _{m ″} —Y ²² —, —Y ²¹ —O—C (═O) —Y ²² — or —Y ²¹ —S (═O) ₂ —O—Y ²² —, wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, and the divalent hydrocarbon group is exemplified in the description of the divalent linking group. And (the divalent hydrocarbon group which may have a substituent).
Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. preferable.
Y ²² is preferably a linear or branched aliphatic hydrocarbon group, and 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.
In the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ″} —Y ²² —, m ″ is an integer of 0 to 3, preferably an integer of 0 to 2, Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ″} —Y ²² — is represented by the formula —Y ²¹ —C (═O) —O—Y ²² —. Especially preferred are groups represented by the formula — (CH ₂ ) _{a ′} —C (═O) —O— (CH ₂ ) _{b ′} —, wherein a ′ is 1 to It is an integer of 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1. b ′ is an integer of 1 to 10, and 1 to 8 An integer of 1 is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is more preferable, and 1 is most preferable.

Ya ²¹ is preferably a single bond, an ester bond [—C (═O) —O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof. .

In the formula (a2-1), Ra ²¹ is a lactone-containing cyclic group, an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group.
The lactone-containing cyclic group, -SO ₂ -containing cyclic group, and carbonate-containing cyclic group in Ra ²¹ are each represented by the general formulas (a2-r-1) to (a2-r-7) described above. Groups represented by general formulas (a5-r-1) to (a5-r-4), groups represented by general formulas (ax3-r-1) to (ax3-r-3), respectively. Are preferable.
Of these, Ra ²¹ is preferably a lactone-containing polycyclic group, a —SO ₂ — containing polycyclic group, or a carbonate-containing polycyclic group. By selecting these polycyclic groups, the resulting photosensitive resin film is particularly improved in all of resistance to solvents, heat resistance, and solubility in an alkaline developer.
Among them, a lactone-containing polycyclic group or a —SO ₂ — containing polycyclic group is preferable, and a group represented by the general formula (a2-r-2) or (a5-r-1) is more preferable. The group represented by the general formula (a2-r-2) is particularly preferable.

As the structural unit (a2) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
When the component (A1) has the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 80 mol% with respect to the total of all the structural units constituting the component (A1). It is more preferably 10 to 70 mol%, further preferably 10 to 65 mol%, particularly preferably 10 to 60 mol%.
By setting the proportion of the structural unit (a2) to be equal to or higher than the lower limit value, the effect of containing the structural unit (a2) can be sufficiently obtained, and by setting the ratio to the upper limit value or less, a balance with other structural units is obtained. And various lithographic properties and pre-pattern shapes are better.

Structural unit (a3):
The structural unit (a3) is a structural unit (excluding those corresponding to the structural unit (a1) or the structural unit (a2)) containing a polar group-containing aliphatic hydrocarbon group.
When the component (A1) has the structural unit (a3), the hydrophilicity of the component (A) increases, which contributes to the improvement of resolution.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a hydroxy group, and the like, and a hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group. For example, a resin for a resist composition for an ArF excimer laser can be appropriately selected from those proposed. The cyclic group is preferably a polycyclic group, and more preferably 7 to 30 carbon atoms.
Among them, a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted with a hydroxy group Is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane and the like. Specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, there are groups in which two or more hydrogen atoms have been removed from adamantane, groups in which two or more hydrogen atoms have been removed from norbornane, and groups in which two or more hydrogen atoms have been removed from tetracyclododecane. Industrially preferable.

The structural unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any structural unit can be used.
The structural unit (a3) is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and includes a polar group-containing aliphatic hydrocarbon group A structural unit is preferred.
The structural unit (a3) is derived from a hydroxyethyl ester of acrylic acid when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms. When the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the structural unit represented by the formula (a3-2), the formula ( The structural unit represented by a3-3) is preferable.

［式中、Ｒは前記と同じであり、ｊは１〜３の整数であり、ｋは１〜３の整数であり、ｔ’は１〜３の整数であり、ｌは１〜５の整数であり、ｓは１〜３の整数である。］

[Wherein, R is as defined above, j is an integer of 1 to 3, k is an integer of 1 to 3, t ′ is an integer of 1 to 3, and l is an integer of 1 to 5] And s is an integer of 1 to 3. ]

In formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, it is preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.
j is preferably 1, and it is particularly preferred that the hydroxyl group is bonded to the 3-position of the adamantyl group.

In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norbornyl group.
In formula (a3-3), t ′ is preferably 1. l is preferably 1. s is preferably 1. These preferably have a 2-norbornyl group or a 3-norbornyl group bonded to the terminal of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group.

As the structural unit (a3) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
When the component (A1) has the structural unit (a3), the proportion of the structural unit (a3) is preferably 5 to 50 mol% with respect to the total of all the structural units constituting the resin component (A1). 5 to 40 mol% is more preferable, and 5 to 25 mol% is more preferable.
By setting the proportion of the structural unit (a3) to the lower limit value or more, the effect of including the structural unit (a3) can be sufficiently obtained, and by setting the proportion of the structural unit (a3) to the upper limit value or less, balance with other structural units can be obtained. It becomes easy.

Structural unit (a4):
The structural unit (a4) is a structural unit containing an acid non-dissociable aliphatic cyclic group.
When the component (A1) has the structural unit (a4), the hydrophobicity of the component (A) is increased. The improvement in hydrophobicity is considered to contribute to the improvement in resolution, pre-pattern shape, etc., particularly in the case of organic solvent development.
The “acid non-dissociable cyclic group” in the structural unit (a4) is obtained when an acid is generated from the photosensitive resin composition by exposure (for example, when an acid is generated from the component (A) or the component (B) described later). And a cyclic group remaining in the structural unit as it is without dissociation even when the acid acts.
As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing a non-acid-dissociable aliphatic cyclic group is preferable. Examples of the cyclic group include those similar to those exemplified for the structural unit (a1), for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser), etc. A number of hitherto known materials can be used as the resin component of the resist composition.
In particular, at least one selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is preferable in terms of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
Specific examples of the structural unit (a4) include structural units represented by general formulas (a4-1) to (a4-7) shown below.

［式中、Ｒ^αは前記と同じである。］

[Wherein, R ^α is the same as defined above. ]

The structural unit (a4) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a4), the proportion of the structural unit (a4) is preferably 1 to 30 mol% with respect to the total of all the structural units constituting the component (A1). 3-20 mol% is more preferable.
By setting the proportion of the structural unit (a4) to the lower limit value or more, the effect of containing the structural unit (a4) can be sufficiently obtained, and by setting the proportion of the structural unit (a4) to the upper limit value or less, balance with other structural units can be obtained. It becomes easy.

As the component (A1), one type may be used alone, or two or more types may be used in combination.
The component (A1) is a polymer compound having the structural unit (a1), and the component (A1) includes a polymer compound having the structural unit (a1) and the structural unit (a2), and the structural unit (a1). And a polymer compound having a structural unit (a1), a structural unit (a2) and a structural unit (a3), a structural unit (a1), a structural unit (a2) and a structural unit A polymer compound having the unit (a3) and the structural unit (a4) is preferable.
In this embodiment, the polymer (A1) is particularly preferably a polymer compound having the structural unit (a1) and the structural unit (a2).

The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography (GPC)) of the component (A1) is not particularly limited, preferably 5000 to 50000, more preferably 8000 to 30000, and 900 to 900 20000 is most preferred. If it is below the upper limit of this range, the solubility of the photosensitive resin composition in the solvent (component (S) described later) is further increased, and if it is above the lower limit of this range, the pre-pattern cross-sectional shape is better. It becomes.
The molecular weight dispersity (Mw / Mn) of the component (A1) is not particularly limited, and is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and most preferably 1.0 to 3.0. preferable.

In the photosensitive resin composition used in this embodiment, the component (A) may be used alone or in combination of two or more.
As the component (A), a polymer compound other than the component (A1) (hereinafter, this polymer compound is referred to as “component (A2)”) may be used, or may be used in combination with the component (A1).
The component (A2) is not particularly limited, and is conventionally known as a substrate component for a chemically amplified resist composition (for example, for ArF excimer laser, for KrF excimer laser (preferably ArF excimer laser). Base resin) and the like may be arbitrarily selected and used.
The content of the component (A) in the photosensitive resin composition may be adjusted according to the thickness of the photosensitive resin film to be formed.

Other components In addition to the above component (A), the photosensitive resin composition used in this embodiment further includes an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as “component (B)”). ) May be contained.

-(B) component (B) It does not specifically limit as a component, What has been proposed as an acid generator for chemical amplification type resists until now can be used.
Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and diazomethanes such as poly (bissulfonyl) diazomethanes. Examples include an acid generator, a nitrobenzyl sulfonate acid generator, an imino sulfonate acid generator, and a disulfone acid generator. Of these, it is preferable to use an onium salt acid generator.

  Examples of the onium salt-based acid generator include a compound represented by the following general formula (b-1) (hereinafter also referred to as “(b-1) component”) and a general formula (b-2). A compound (hereinafter also referred to as “(b-2) component”) or a compound represented by the general formula (b-3) (hereinafter also referred to as “(b-3) component”) can be used.

［式中、Ｒ^１０１、Ｒ^１０４〜Ｒ^１０８はそれぞれ独立に置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である。Ｒ^１０４、Ｒ^１０５は、相互に結合して環を形成していてもよい。Ｒ^１０２はフッ素原子または炭素数１〜５のフッ素化アルキル基である。Ｙ^１０１は単結合または酸素原子を含む２価の連結基である。Ｖ^１０１〜Ｖ^１０３はそれぞれ独立に単結合、アルキレン基、またはフッ素化アルキレン基である。Ｌ^１０１〜Ｌ^１０２はそれぞれ独立に単結合または酸素原子である。Ｌ^１０３〜Ｌ^１０５はそれぞれ独立に単結合、−ＣＯ−又は−ＳＯ_２−である。ｍは１以上の整数であって、Ｍ’^ｍ＋はｍ価のオニウムカチオンである。］

[Wherein, R ¹⁰¹ and R ^{104 to} R ¹⁰⁸ each independently has a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. A chain alkenyl group which may be present. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ^{101 to} V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group. L ^{101 to} L ¹⁰² are each independently a single bond or an oxygen atom. L ^{103 to} L ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —. m is an integer of 1 or more, and M ′ ^{m +} is an m-valent onium cation. ]

... Anion part (b-1) Anion part of component:
In formula (b-1), R ¹⁰¹ may have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. A chain alkenyl group.

Cyclic group which may have a substituent:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group for R ¹⁰¹ is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring of the aromatic hydrocarbon group in R ¹⁰¹ include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings substituted with a heteroatom. An aromatic heterocyclic ring is mentioned. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specifically, the aromatic hydrocarbon group in R ¹⁰¹ is a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and one of the hydrogen atoms of the aromatic ring is alkylene. And a group substituted with a group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

Examples of the cyclic aliphatic hydrocarbon group for R ¹⁰¹ include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group is linear or branched Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched 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. As the monocyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane is preferable. 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 obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms. Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
Among these, the cyclic aliphatic hydrocarbon group for R ¹⁰¹ is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or polycycloalkane, and more preferably a group obtained by removing one hydrogen atom from a polycycloalkane. An adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

The linear or branched aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 4 carbon atoms. Is more preferable, and 1-3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

In addition, the cyclic hydrocarbon group for R ¹⁰¹ may contain a hetero atom such as a heterocyclic ring. Specifically, the lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), and the general formulas (a5-r-1) to (a5-r- -SO 2 respectively represented by 4) _- containing cyclic group, heterocyclic group listed other less like.

Examples of the substituent in the cyclic hydrocarbon group of R ¹⁰¹ include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group (—C (═O) —), an ether bond (—O—). ), An ester bond (—C (═O) —O—), a nitro group, and the like.
The alkyl group as a 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 a 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. Most preferred is an ethoxy group.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group as a substituent, a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, and the like And a group substituted with a halogen atom.
A carbonyl group (—C (═O) —), an ether bond (—O—), and an ester bond (—C (═O) —O—) as a substituent group are methylene groups ( It is a group that substitutes —CH ₂ —).

A chain-like alkyl group which may have a substituent:
The chain alkyl group for R ¹⁰¹ may be either linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group Group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group and the like.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.

A chain-like alkenyl group which may have a substituent:
The chain alkenyl group for R ¹⁰¹ may be either linear or branched, preferably has 2 to 10 carbon atoms, more preferably 2 to 5, still more preferably 2 to 4, more preferably 3 Is particularly preferred. 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 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group and the like.
Among the above, the chain alkenyl group is more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.

Examples of the substituent in the chain alkyl group or alkenyl group of R ¹⁰¹ include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group (—C (═O) —), an ether bond (—O—). ), An ester bond (—C (═O) —O—), a nitro group, an amino group, the cyclic group in R ^{101, and} the like.
The alkoxy group as a 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. Most preferred is an ethoxy group.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group as a substituent, a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, and the like And a group substituted with a halogen atom.
A carbonyl group (—C (═O) —), an ether bond (—O—), or an ester bond (—C (═O) —O—) as a substituent constitutes a chain alkyl group or alkenyl group. It is a group that substitutes a methylene group (—CH ₂ —).

Among these, R ¹⁰¹ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and lactones represented by the above formulas (a2-r-1) to (a2-r-7), respectively. The containing cyclic group, the —SO ₂ -containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4), respectively, and the like are preferable.

In formula (b-1), Y ¹⁰¹ represents a single bond or a divalent linking group containing an oxygen atom.
When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, Y ¹⁰¹ may contain an atom other than an oxygen atom. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.
Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond: —O—), an ester bond (—C (═O) —O—), and an oxycarbonyl group (—O—C (═O). )-), Amide bond (—C (═O) —NH—), carbonyl group (—C (═O) —), carbonate bond (—O—C (═O) —O—), etc. A combination of a non-hydrocarbon oxygen atom-containing linking group and an alkylene group; and the like. A sulfonyl group (—SO ₂ —) may be further linked to the combination. Examples of the combination include linking groups represented by the following formulas (y-al-1) to (y-al-7), respectively.

［式中、Ｖ’^１０１は単結合または炭素数１〜５のアルキレン基であり、Ｖ’^１０２は炭素数１〜３０の２価の飽和炭化水素基である。］

[Wherein, V ′ ¹⁰¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, and V ′ ¹⁰² is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. ]

The divalent saturated hydrocarbon group for V ′ ¹⁰² is preferably an alkylene group having 1 to 30 carbon atoms.

The alkylene group for V ′ ¹⁰¹ and V ′ ¹⁰² may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferred.
Specific examples of the alkylene group in V ′ ¹⁰¹ and V ′ ¹⁰² include a methylene group [—CH ₂ —]; —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as ethylene Groups [—CH ₂ CH ₂ —]; —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, —C (CH ₃ ) ₂ CH ₂ —, —CH (CH ₂ CH - ₃₎ CH ₂ alkyl groups such as, trimethylene group (n- propylene _{group) [- CH 2 CH 2 CH} 2 -]; - CH (CH 3) CH 2 CH 2 -, - CH 2 CH (CH 3) CH ₂ - and the like alkyl trimethylene group; tetramethylene _{[-CH 2 CH 2 CH 2 CH} 2 -]; - CH (CH 3) CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 CH 2 - alkyl tetramethylene group and the like; pentamethylene group _{[-CH 2 CH 2 CH 2 CH} 2 CH 2 -] , and the like.
Moreover, some methylene groups in the alkylene group in V ′ ¹⁰¹ or V ′ ¹⁰² may be substituted with a C 5-10 divalent aliphatic cyclic group. The aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group of Ra ′ ^{3 in} the formula (a1-r-1). 1,5-adamantylene group or 2,6-adamantylene group is more preferable.

Y ¹⁰¹ is preferably a divalent linking group containing an ester bond or an ether bond, and linking groups represented by the above formulas (y-al-1) to (y-al-5) are preferred.

In formula (b-1), V ¹⁰¹ represents a single bond, an alkylene group, or a fluorinated alkylene group. The alkylene group and fluorinated alkylene group for V ¹⁰¹ preferably have 1 to 4 carbon atoms. ^Examples of the fluorinated alkylene group for V ¹⁰¹ include groups in which some or all of the hydrogen atoms of the alkylene group for V ¹⁰¹ have been substituted with fluorine atoms. Among ^{them, V 101} is preferably a single bond, or a fluorinated alkylene group having 1 to 4 carbon atoms.

In formula (b-1), R ¹⁰² represents a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R ¹⁰² is preferably a fluorine atom or a C 1-5 perfluoroalkyl group, and more preferably a fluorine atom.

(B-1) Specific examples of the anion moiety of the component, for example, if the Y ¹⁰¹ is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethane sulfonate anion or perfluorobutane sulfonate anion can be exemplified; Y ¹⁰¹ is In the case of a divalent linking group containing an oxygen atom, anions represented by any one of the following formulas (an-1) to (an-3) can be mentioned.

［式中、Ｒ”^１０１は、置換基を有していてもよい脂肪族環式基、前記式（ｒ−ｈｒ−１）〜（ｒ−ｈｒ−６）でそれぞれ表される基、又は置換基を有していてもよい鎖状のアルキル基であり；Ｒ”^１０２は、置換基を有していてもよい脂肪族環式基、前記式（ａ２−ｒ−１）〜（ａ２−ｒ−７）でそれぞれ表されるラクトン含有環式基、又は前記一般式（ａ５−ｒ−１）〜（ａ５−ｒ−４）でそれぞれ表される−ＳＯ_２−含有環式基であり；Ｒ”^１０３は、置換基を有していてもよい芳香族環式基、置換基を有していてもよい脂肪族環式基、又は置換基を有していてもよい鎖状のアルケニル基であり；ｖ”はそれぞれ独立に０〜３の整数であり、ｑ”はそれぞれ独立に１〜２０の整数であり、ｔ”は１〜３の整数であり、ｎ”は０または１である。］

[Wherein R ″ ¹⁰¹ represents an aliphatic cyclic group which may have a substituent, a group represented by each of the above formulas (r-hr-1) to (r-hr-6), or a substituent. A chain-like alkyl group which may have a group; R ″ ¹⁰² represents an aliphatic cyclic group which may have a substituent, the above formulas (a2-r-1) to (a2-r); lactone-containing cyclic group represented respectively by -7), or the formula (a5-r-1) ~ (a5-r-4) with -SO ₂ respectively represented - be-containing cyclic group; R ¹⁰³ is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. Yes; v ″ is independently an integer of 0 to 3, q ″ is independently an integer of 1 to 20, t ″ is an integer of 1 to 3, and n ″ is 0 or 1 a is.]

The aliphatic cyclic group which may have a substituent of R ″ ¹⁰¹ , R ″ ¹⁰² and R ″ ¹⁰³ is preferably the group exemplified as the cyclic aliphatic hydrocarbon group in R ¹⁰¹ . Examples of the substituent include the same substituents that may be substituted for the cyclic aliphatic hydrocarbon group in R ¹⁰¹ .

The aromatic cyclic group which may have a substituent in R ″ ¹⁰³ is preferably the group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R ¹⁰¹ . , R ¹⁰¹ and the same substituents that may be substituted for the aromatic hydrocarbon group.

R have a substituent in "which may chain substituted at ¹⁰¹ alkyl group, wherein preferably a group exemplified as chain alkyl group in R ¹⁰¹ .R" ¹⁰³ The good chain alkenyl group is preferably the group exemplified as the chain alkenyl group in R ¹⁰¹ .

(B-2) Anion part of component:
In formula (b-2), R ¹⁰⁴ and R ¹⁰⁵ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. A chain alkenyl group optionally having the same meaning as R ¹⁰¹ in formula (b-1). However, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.
R ¹⁰⁴ and R ¹⁰⁵ are preferably a chain alkyl group which may have a substituent, and are a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. It is more preferable.
The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and still more preferably 1 to 3 carbon atoms. The reason for the carbon number of the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is that the solubility of the photosensitive resin composition in the solvent (component (S) described later) is good within the range of the carbon number. Therefore, the smaller the better. In addition, in the chain alkyl group of R ¹⁰⁴ and R ^105, the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and against high-energy light and electron beams of 200 nm or less Since transparency improves, it is preferable. The proportion of fluorine atoms in the chain alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. Perfluoroalkyl group.
In formula (b-2), V ¹⁰² and V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and each of them is the same as V ¹⁰¹ in formula (b-1). Can be mentioned.
In formula (b-2), L ^{101 to} L ¹⁰² each independently represents a single bond or an oxygen atom.

(B-3) Anion part of component:
In formula (b-3), R ^{106 to} R ¹⁰⁸ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. A chain alkenyl group optionally having the same meaning as R ¹⁰¹ in formula (b-1).
L ^{103 to} L ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —.

... Cation moiety In formulas (b-1), (b-2), and (b-3), ^{M'm +} is an m-valent onium cation, and a sulfonium cation and an iodonium cation are preferable. Specifically, organic cations represented by the following general formulas (ca-1) to (ca-4) are preferable.

［式中、Ｒ^２０１〜Ｒ^２０７、およびＲ^２１１〜Ｒ^２１２は、それぞれ独立に置換基を有していてもよいアリール基、アルキル基またはアルケニル基を表し、Ｒ^２０１〜Ｒ^２０３、Ｒ^２０６〜Ｒ^２０７、Ｒ^２１１〜Ｒ^２１２は、相互に結合して式中のイオウ原子と共に環を形成してもよい。Ｒ^２０８〜Ｒ^２０９はそれぞれ独立に水素原子または炭素数１〜５のアルキル基を表し、Ｒ^２１０は置換基を有していてもよいアリール基、アルキル基、アルケニル基、又は−ＳＯ_２−含有環式基であり、Ｌ^２０１は−Ｃ（＝Ｏ）−または−Ｃ（＝Ｏ）−Ｏ−を表し、Ｙ^２０１は、それぞれ独立に、アリーレン基、アルキレン基またはアルケニレン基を表し、ｘは１または２であり、Ｗ^２０１は（ｘ＋１）価の連結基を表す。］

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

Examples of the aryl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
The alkyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² is a chain or cyclic alkyl group and preferably has 1 to 30 carbon atoms.
The alkenyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² preferably has 2 to 10 carbon atoms.
Examples of the substituent that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, And groups represented by formulas (ca-r-1) to (ca-r-7), respectively.

［式中、Ｒ’^２０１はそれぞれ独立に、水素原子、置換基を有していてもよい環式基、鎖状のアルキル基、または鎖状のアルケニル基である。］

[Wherein, R ′ ²⁰¹ each independently represents a hydrogen atom, an optionally substituted cyclic group, a chain alkyl group, or a chain alkenyl group. ]

The cyclic group which may have a substituent of R ′ ^201, the chain alkyl group which may have a substituent, or the chain alkenyl group which may have a substituent are as described above. In addition to the same as R ^{101 in} the formula (b-1), the cyclic group which may have a substituent or the chain alkyl group which may have a substituent may include: The same thing as the acid dissociable group represented by the above-mentioned formula (a1-r-2) is also mentioned.

^{R 201 ~R 203, R 206 ~R} 207, R 211 ~R 212 , when bonded to each other to form a ring with the sulfur atom, a sulfur atom, an oxygen atom, or a hetero atom such as nitrogen atom, carbonyl _{group, -SO -, - SO 2 -} , - SO 3 -, - COO -, - CONH- , or -N _(R N) - (. the _{R N} is an alkyl group having 1 to 5 carbon atoms), etc. You may couple | bond through the functional group of. As the ring to be formed, one ring containing a sulfur atom in the ring skeleton in the formula is preferably a 3- to 10-membered ring, particularly a 5- to 7-membered ring, including the sulfur atom. preferable. Specific examples of the ring formed include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxathiin ring, tetrahydro A thiophenium ring, a tetrahydrothiopyranium ring, etc. are mentioned.

R ^{208 to} R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. A ring may be formed.

R ²¹⁰ may have an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. -SO ₂ - containing cyclic group.
The aryl group in R ^210, include unsubstituted aryl group having 6 to 20 carbon atoms, a phenyl group, a naphthyl group.
The alkyl group for R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R ²¹⁰ preferably has 2 to 10 carbon atoms.
The —SO ₂ — containing cyclic group which may have a substituent in R ²¹⁰ is the same as the “—SO ₂ — containing cyclic group” of Ra ^{21 in} the aforementioned general formula (a2-1). The group represented by the general formula (a5-r-1) described above is preferable.

Y ²⁰¹ each independently represents an arylene group, an alkylene group or an alkenylene group.
Examples of the arylene group for Y ²⁰¹ include a group in which one hydrogen atom has been removed from the aryl group exemplified as the aromatic hydrocarbon group for R ¹⁰¹ in the aforementioned formula (b-1).
As the alkylene group and alkenylene group for Y ²⁰¹ , the same aliphatic hydrocarbon groups as divalent hydrocarbon groups for Va ¹ in the aforementioned general formula (a1-1) can be mentioned.

In the formula (ca-4), x is 1 or 2.
W ²⁰¹ is a (x + 1) valent, that is, a divalent or trivalent linking group.
The divalent linking group in W ²⁰¹ is preferably a divalent hydrocarbon group which may have a substituent, and examples thereof include the same hydrocarbon groups as those of Ya ²¹ in the general formula (a2-1). . The divalent linking group in W ²⁰¹ may be linear, branched or cyclic, and is preferably cyclic. Of these, a group in which two carbonyl groups are combined at both ends of the arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
^Examples of the trivalent linking group in W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group in W ²⁰¹ , a group in which the divalent linking group is further bonded to the divalent linking group, and the like. Can be mentioned. The trivalent linking group in W ²⁰¹ is preferably a group in which two carbonyl groups are bonded to an arylene group.

  Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-67), respectively.

［式中、ｇ１、ｇ２、ｇ３は繰返し数を示し、ｇ１は１〜５の整数であり、ｇ２は０〜２０の整数であり、ｇ３は０〜２０の整数である。］

[Wherein, g1, g2, and g3 represent the number of repetitions, g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20. ]

［式中、Ｒ”^２０１は水素原子又は置換基であって、置換基としては前記Ｒ^２０１〜Ｒ^２０７、およびＲ^２１０〜Ｒ^２１２が有していてもよい置換基として挙げたものと同様である。］

[Wherein R ″ ²⁰¹ is a hydrogen atom or a substituent, and the substituent is the same as the substituents that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have. is there.]

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

  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).

  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).

Among these, the cation part [M ′ ^{m +} ] is preferably a cation represented by the general formula (ca-1), and each cation represented by the formulas (ca-1-1) to (ca-1-67). Is more preferable.

As the component (B), one type of acid generator described above may be used alone, or two or more types may be used in combination.
Among these, it is particularly preferable to use the component (b-1) as the component (B).
When the photosensitive resin composition used in this embodiment contains the component (B), the content of the component (B) is preferably 0.5 to 60 parts by mass with respect to 100 parts by mass of the component (A). -50 mass parts is more preferable, and 1-40 mass parts is further more preferable.
(B) By making content of a component into the said range, pre-pattern formation is fully performed. Moreover, it is preferable because a uniform solution is easily obtained and the storage stability is improved.

-(D) component In addition to (A) component or in addition to (A) component and (B) component, the photosensitive resin composition used by this aspect is further an acid diffusion control agent component (following). "(D) component") may be contained.
The component (D) acts as a quencher (acid diffusion controller) that traps acid generated by exposure from the components (A) and (B).
The component (D) may be a photodegradable base (D1) (hereinafter referred to as “component (D1)”) that is decomposed by exposure and loses acid diffusion controllability, and includes a component that does not correspond to the component (D1). It may be a nitrogen organic compound (D2) (hereinafter referred to as “component (D2)”).

... About (D1) component By forming it as the photosensitive resin composition containing (D1) component, when forming a pre-pattern, the contrast of an exposed part and an unexposed part can be improved.
The component (D1) is not particularly limited as long as it is decomposed by exposure and loses acid diffusion controllability, and is a compound represented by the following general formula (d1-1) (hereinafter referred to as “(d1-1) component”). ), A compound represented by the following general formula (d1-2) (hereinafter referred to as “(d1-2) component”) and a compound represented by the following general formula (d1-3) (hereinafter referred to as “(d1- One or more compounds selected from the group consisting of “3) component”) are preferred.
The components (d1-1) to (d1-3) are decomposed in the exposed portion and lose acid diffusion controllability (basicity), and thus do not act as a quencher, and act as a quencher in an unexposed portion.

［式中、Ｒｄ^１〜Ｒｄ^４は置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である。ただし、式（ｄ１−２）中のＲｄ^２における、Ｓ原子に隣接する炭素原子にはフッ素原子は結合していないものとする。Ｙｄ^１は単結合または２価の連結基である。ｍは１以上の整数であって、Ｍ^ｍ＋はそれぞれ独立にｍ価の有機カチオンである。］

[Wherein Rd ^{1 to} Rd ⁴ are a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. Of the alkenyl group. However, a fluorine atom is not bonded to a carbon atom adjacent to the S atom in Rd ² in the formula (d1-2). Yd ¹ is a single bond or a divalent linking group. m is an integer of 1 or more, and M ^{m +} is each independently an m-valent organic cation. ]

{(D1-1) component}
(D1-1) Anion part of component:
In formula (d1-1), Rd ¹ is a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a chain that may have a substituent. And the same as R ¹⁰¹ in the formula (b-1).
Among these, Rd ¹ may have an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a substituent. A chain alkyl group is preferred. The substituent that these groups may have is preferably a hydroxyl group, a fluorine atom or a fluorinated alkyl group.
As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is more preferable.
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, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Linear alkyl groups such as nonyl and decyl; 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl A branched alkyl group such as a group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group.

When the chain alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the fluorinated alkyl group preferably has 1 to 11 carbon atoms, more preferably 1 to 8 carbon atoms. ~ 4 is more preferred. The fluorinated alkyl group may contain an atom other than a fluorine atom. Examples of atoms other than fluorine atoms include oxygen atoms, carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.
Rd ¹ is preferably a fluorinated alkyl group in which some or all of the hydrogen atoms constituting the linear alkyl group are substituted by fluorine atoms, and the hydrogen atom constituting the linear alkyl group It is preferable that all are fluorinated alkyl groups (linear perfluoroalkyl groups) substituted with fluorine atoms.

  Preferred specific examples of the anion moiety of the component (d1-1) are shown below.

(D1-1) Cation part of component:
In formula (d1-1), M ^{m +} is an m-valent organic cation.
As the organic cation of M ^{m +} , those similar to the cations represented by the general formulas (ca-1) to (ca-4) are preferably exemplified, and the formulas (ca-1-1) to (ca Cations represented by -1-67) are more preferable.
As the component (d1-1), one type may be used alone, or two or more types may be used in combination.

{(D1-2) component}
(D1-2) component anion moiety:
In formula (d1-2), Rd ² may have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. Examples of the chain alkenyl group include those similar to R ¹⁰¹ in the formula (b-1).
However, a fluorine atom is not bonded to a carbon atom adjacent to the S atom in Rd ² (not fluorine-substituted). Thereby, the anion of (d1-2) component turns into a moderate weak acid anion, and the quenching ability as (D) component improves.
Rd ² is preferably an aliphatic cyclic group which may have a substituent, and a group in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like. (It may have a substituent); it is more preferably a group obtained by removing one or more hydrogen atoms from camphor or the like.
The hydrocarbon group of Rd ² may have a substituent, and examples of the substituent include a hydrocarbon group (aromatic hydrocarbon group, aliphatic hydrocarbon group) in Rd ¹ of the formula (d1-1). The same thing as the substituent which may have is mentioned.

  Preferred specific examples of the anion moiety of the component (d1-2) are shown below.

(D1-2) Cation part of component:
In formula (d1-2), M ^{m +} is an m-valent organic cation, and is the same as M ^{m +} in formula (d1-1).
As the component (d1-2), one type may be used alone, or two or more types may be used in combination.

{(D1-3) component}
(D1-3) Anion part of component:
In formula (d1-3), Rd ³ represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. A alkenyl group having the same shape as R ¹⁰¹ in the formula (b-1), and a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group. preferable. Among them, a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group for Rd ¹ is more preferable.

In formula (d1-3), Rd ⁴ may have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. Examples of the chain alkenyl group include those similar to R ¹⁰¹ in the formula (b-1).
Among these, an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group which may have a substituent is preferable.
The alkyl group in Rd ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group. Tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. A part of the hydrogen atoms of the alkyl group of Rd ⁴ may be substituted with a hydroxyl group, a cyano group, or the like.
The alkoxy group in Rd ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n- Examples include butoxy group and tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferable.

Examples of the alkenyl group for Rd ⁴ include the same as those for R ¹⁰¹ in the above formula (b-1), and a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group are preferable. These groups may further have, as a substituent, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

Examples of the cyclic group for Rd ⁴ include those similar to R ¹⁰¹ in the above formula (b-1), such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. An alicyclic group excluding one or more hydrogen atoms, or an aromatic group such as a phenyl group or a naphthyl group is preferred. When Rd ⁴ is an alicyclic group, the photosensitive resin composition dissolves well in an organic solvent, thereby improving the lithography properties. Further, when Rd ⁴ is an aromatic group, in the lithography using EUV or the like as an exposure light source, the photosensitive resin composition is excellent in light absorption efficiency, and sensitivity and lithography characteristics are improved.

In formula (d1-3), Yd ¹ represents a single bond or a divalent linking group.
The divalent linking group in Yd ¹ is not particularly limited, but may be a divalent hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group) which may have a substituent, or a hetero atom containing 2 Valent linking groups and the like. Each of these includes a divalent hydrocarbon group which may have a substituent and a hetero atom which are mentioned in the description of the divalent linking group of Ya ²¹ in the formula (a2-1). The thing similar to a valent coupling group is mentioned.
Yd ¹ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is preferably a linear or branched alkylene group, and more preferably a methylene group or an ethylene group.

  Preferred specific examples of the anion moiety of the component (d1-3) are shown below.

(D1-3) Cation part of component:
In formula (d1-3), M ^{m +} is an m-valent organic cation, and is the same as M ^{m +} in formula (d1-1).
As the component (d1-3), one type may be used alone, or two or more types may be used in combination.

As the component (D1), only one of the above components (d1-1) to (d1-3) may be used, or two or more may be used in combination.
When the photosensitive resin composition used in this embodiment contains the component (D1), the content of the component (D1) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). Is preferably 0.5-8 parts by mass, and more preferably 1-8 parts by mass.
When the content of the component (D1) is equal to or more than the preferable lower limit value, it is easy to obtain a prepattern having particularly good lithography characteristics and shape. On the other hand, when it is not more than the upper limit value, the sensitivity can be maintained well and the throughput is also excellent.

(Production method of component (D1))
The manufacturing method of said (d1-1) component and (d1-2) component is not specifically limited, It can manufacture by a well-known method.
Moreover, the manufacturing method of (d1-3) component is not specifically limited, For example, it manufactures similarly to the method of US2012-0149916 gazette.

... (D2) component As an acid diffusion controlling agent component, you may contain the nitrogen-containing organic compound component (henceforth "(D2) component") which does not correspond to said (D1) component.
The component (D2) is not particularly limited as long as it functions as an acid diffusion controller and does not correspond to the component (D1), and any known component may be used. Of these, aliphatic amines, and particularly, secondary aliphatic amines and tertiary aliphatic amines are preferable.
An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms.
Examples of the aliphatic amine include an amine (alkyl amine or alkyl alcohol amine) or a cyclic amine in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms.
Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, Li isopropanolamine, di -n- octanol amines, alkyl alcohol amines tri -n- octanol amine. Among these, a trialkylamine having 5 to 10 carbon atoms is more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable. Specifically, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5. 4.0] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.

  Other aliphatic amines include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2 -(1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2- (2-hydroxy Ethoxy) ethoxy} ethyl] amine, triethanolamine triacetate and the like, and triethanolamine triacetate is preferable.

As the component (D2), an aromatic amine may be used.
Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine and the like.

(D2) A component may be used independently and may be used in combination of 2 or more type.
When the photosensitive resin composition used in this embodiment contains the component (D2), the component (D2) is usually used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). . By setting it as the above range, the pattern shape, the stability over time and the like are improved.

.. (E) component The photosensitive resin composition used in this embodiment includes an organic carboxylic acid as an optional component for the purpose of preventing sensitivity deterioration and improving the shape of the pattern, stability over time, etc. At least one compound (E) selected from the group consisting of phosphorus oxoacids and derivatives thereof (hereinafter referred to as “component (E)”) can be contained.
As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
Examples of phosphorus oxo acids include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferable.
Examples of the oxo acid derivative of phosphorus include esters in which the hydrogen atom of the oxo acid is substituted with a hydrocarbon group, and the hydrocarbon group includes an alkyl group having 1 to 5 carbon atoms and 6 to 6 carbon atoms. 15 aryl groups and the like.
Examples of phosphoric acid derivatives include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
Examples of phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester.
Examples of phosphinic acid derivatives include phosphinic acid esters and phenylphosphinic acid.
(E) A component may be used individually by 1 type and may use 2 or more types together.
When the photosensitive resin composition used in this embodiment contains the component (E), the component (E) is usually used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). It is done.

.. (F) Component The photosensitive resin composition used in this embodiment may contain a fluorine additive (hereinafter referred to as “component (F)”) in order to impart water repellency to the photosensitive resin film. Good.
Examples of the component (F) include those described in JP 2010-002870 A, JP 2010-032994 A, JP 2010-277043 A, JP 2011-13569 A, and JP 2011-128226 A. These fluorine-containing polymer compounds can be used.
More specifically, examples of the component (F) include a polymer having a structural unit (f1) represented by the following formula (f1-1). Examples of the polymer include a polymer (homopolymer) composed only of the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1). A copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1). Here, the structural unit (a1) copolymerized with the structural unit (f1) is preferably a structural unit derived from 1-ethyl-1-cyclooctyl (meth) acrylate.

［式中、Ｒは前記と同様であり、Ｒｆ^１０２およびＲｆ^１０３はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜５のアルキル基、又は炭素数１〜５のハロゲン化アルキル基を表し、Ｒｆ^１０２およびＲｆ^１０３は同じであっても異なっていてもよい。ｎｆ^１は１〜５の整数であり、Ｒｆ^１０１はフッ素原子を含む有機基である。］

[Wherein, R is as defined above, and Rf ¹⁰² and Rf ¹⁰³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. , Rf ¹⁰² and Rf ¹⁰³ may be the same or different. nf ¹ is an integer of ¹ to 5, and Rf ¹⁰¹ is an organic group containing a fluorine atom. ]

In formula (f1-1), R bonded to the α-position carbon atom is the same as described above. R is preferably a hydrogen atom or a methyl group.
In formula (f1-1), examples of the halogen atom for Rf ¹⁰² and Rf ¹⁰³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. Examples of the alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include the same as the alkyl group having 1 to 5 carbon atoms of R, and a methyl group or an ethyl group is preferable. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. Can be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. The inter alia ^{Rf 102} and ^{Rf 103,} a hydrogen atom, a fluorine atom, or an alkyl group of 1 to 5 carbon atoms is preferable, a hydrogen atom, a fluorine atom, a methyl group or an ethyl group, preferred.
In formula (f1-1), nf ¹ is an integer of ¹ to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

In formula (f1-1), Rf ¹⁰¹ is an organic group containing a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom.
The hydrocarbon group containing a fluorine atom may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms. The carbon number of 1 to 10 is particularly preferable.
The hydrocarbon group containing a fluorine atom preferably has 25% or more of the hydrogen atoms in the hydrocarbon group fluorinated, more preferably 50% or more fluorinated, and 60% or more. Fluorination is particularly preferred because the hydrophobicity of the photosensitive resin film during immersion exposure is increased.
Among ^these, as ^{Rf 101,} particularly preferably a fluorinated hydrocarbon group having 1 to 5 carbon atoms, a trifluoromethyl _{group, -CH 2 -CF 3, -CH 2} -CF 2 -CF 3, -CH (CF 3 ) ₂ , —CH ₂ —CH ₂ —CF ₃ , —CH ₂ —CH ₂ —CF ₂ —CF ₂ —CF ₂ —CF ₃ are most preferred.

(F) As for the mass mean molecular weight (Mw) (polystyrene conversion reference | standard by a gel permeation chromatography), 1000-50000 are preferable, 5000-40000 are more preferable, and 10000-30000 are the most preferable. If it is below the upper limit of this range, the solubility of the photosensitive resin composition in the solvent (component (S) described later) is further increased, and if it is above the lower limit of this range, the pre-pattern cross-sectional shape is better. It becomes.
The molecular weight dispersity (Mw / Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.

(F) A component may be used individually by 1 type and may use 2 or more types together.
When the photosensitive resin composition used in this embodiment contains the component (F), the component (F) is preferably used at a ratio of 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). It is done.

  The photosensitive resin composition used in this embodiment further has miscible additives as desired, for example, additional resins for improving the performance of the photosensitive resin film, dissolution inhibitors, plasticizers, stabilizers, and coloring. An agent, an antihalation agent, a dye, and the like can be appropriately added and contained.

.. (S) Component The photosensitive resin composition used in this embodiment can be produced by dissolving each component used in the composition in an organic solvent (hereinafter sometimes referred to as “(S) component”). it can.
As the component (S), any component can be used as long as it can dissolve each component to be used to form a uniform solution. Conventionally, any one of known solvents for chemically amplified resists can be used. Two or more types can be appropriately selected and used.
For example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; many such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol Monohydric alcohols; compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, monomethyl ether, monoethyl of the polyhydric alcohols or compound having the ester bond Ethers such as ether, monopropyl ether, monobutyl ether and other monoalkyl ethers and monophenyl ether Derivatives of polyhydric alcohols such as compounds having a combination [in these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, methyl lactate Esters such as ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether , Dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. Examples of the solvent include dimethyl sulfoxide (DMSO).
These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Of these, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferable.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is also preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be within the range.
More specifically, when EL or cyclohexanone is blended as the polar solvent, the mass ratio of PGMEA: EL or cyclohexanone is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. . Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7: 3. Furthermore, a mixed solvent of PGMEA, PGME, and cyclohexanone is also preferable.
In addition, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
(S) The usage-amount of a component is not specifically limited, It is a density | concentration which can be apply | coated to a support body etc., and is suitably set according to a coating film thickness. Generally, it is used so that the solid content concentration of the photosensitive resin composition is in the range of 1 to 20% by mass, preferably 2 to 15% by mass.

≪Method for producing structure including phase separation structure≫
In the second aspect of the present invention, a plurality of kinds of patterns are coated on the support on which the pattern comprising the neutralized film is formed by the pattern forming method of the first aspect of the present invention. A structure comprising a phase-separated structure, comprising: a step (4) of forming a layer containing a block copolymer to which a polymer is bonded; and a step (5) of phase-separating the layer containing the block copolymer (5). It is a manufacturing method.
Hereinafter, a method for producing a structure including the phase separation structure of this embodiment will be described with reference to the drawings. However, the present invention is not limited to this.

FIG. 2 shows an embodiment of a method for producing a structure including the phase separation structure of this aspect.
In this embodiment, a block copolymer in which two types of polymers are bonded is used. In FIG. 2, among the blocks constituting the block copolymer, the phase P _A block blocks that are not selectively removed after the separation, the block which is selectively removed to block P _B.
First, the support body 1 in which the pattern which consists of the neutralization film | membrane 3a was formed is prepared (FIG.2 (a): same as FIG.1 (e)).
Next, on the support 1 on which the pattern made of the neutralized film 3a is formed, two kinds of resin compositions containing a block copolymer in which two kinds of polymers are bonded are coated with the two kinds of patterns. A layer 4 containing a block copolymer to which a polymer is bonded is formed (FIG. 2 (b); step (4)).
Next, the layer 4 is annealed. Thus, self-organization proceeds of the block copolymer, a phase 4a made of block P _B, and phase separation, the phase 4b consisting block P _A, (Figure structure 5 is manufactured containing a phase separation structure 2 (c); step (5)).

<Process (4)>
In the step (4), a plurality of types of polymers are bonded so as to cover the pattern on the support on which the pattern made of the neutralized film is formed by the pattern forming method of the first aspect of the present invention. A layer containing the block copolymer is formed.
In this embodiment, the layer 4 containing a block copolymer is formed by, for example, applying a block copolymer solution obtained by dissolving a block copolymer in which two types of polymers are bonded to an organic solvent on the support 1 by spin coating or the like. Can be implemented. At that time, the heating temperature is preferably 180 to 260 ° C., and the heating time is preferably 30 to 600 seconds.
The thickness of the layer 4 containing the block copolymer formed on the support 1 is appropriately determined depending on the molecular weight of the block copolymer and the polymer period, and is generally in the range of 0.5 to 4 times the polymer period. In the present embodiment, the thickness of the layer 4 may be a thickness that can cause phase separation. Specifically, in consideration of the strength and uniformity of the phase separation structure, the thickness is 5 nm or more. It is preferable that the thickness is 10 to 60 nm.

(Block copolymer solution)
The block copolymer solution in this embodiment is obtained by dissolving a block copolymer in which two types of polymers are bonded in an organic solvent.
In the block copolymer solution, the solid content concentration of the block copolymer is preferably 0.2 to 70% by mass, more preferably 0.2 to 50% by mass. If the concentration of the block copolymer is not less than the preferred lower limit value, the block copolymer solution is easily applied uniformly on the support 1. On the other hand, if it is below the preferable upper limit value, the liquid stability of the block copolymer solution can be easily maintained.

Block copolymer A block copolymer is a polymer in which a plurality of types of blocks (partial constituent components in which the same type of structural units are repeatedly bonded) are bonded. There may be two types of blocks constituting the block copolymer (this embodiment), or three or more types.
In this embodiment, the plurality of types of blocks constituting the block copolymer are not particularly limited as long as they are combinations that cause phase separation, but are preferably combinations of blocks that are incompatible with each other. Moreover, it is preferable that the phase which consists of at least 1 type block in the multiple types of block which comprises a block copolymer is a combination which can be selectively removed easily rather than the phase which consists of other types of block.

In the present invention, the “period of the block copolymer” means the period of the phase structure observed when the phase-separated structure is formed, and is the sum of the lengths of the phases that are incompatible with each other. The period of the block copolymer corresponds to the length of one molecule of the block copolymer.
The period of the block copolymer depends on the intrinsic polymerization characteristics such as the degree of polymerization N and the Flory-Huggins interaction parameter χ. That is, the greater the “χN”, the greater the repulsion between different blocks in the block copolymer. For this reason, when χN> 10 (hereinafter referred to as “strength separation limit point”), the repulsion between different types of blocks in the block copolymer is large, and the tendency of phase separation to increase. At the intensity separation limit point, the period of the block copolymer is approximately N ^2/3 χ ^1/6 . That is, the period of the block copolymer is proportional to the degree of polymerization N that correlates with the molecular weight Mn and the molecular weight ratio between different blocks. Therefore, the period of the block copolymer can be easily adjusted by adjusting the composition and the total molecular weight of the block copolymer used.

  As the block copolymer, for example, a block copolymer in which a block of a structural unit derived from styrene or a derivative thereof and a block of a structural unit derived from an (α-substituted) acrylate ester are combined; from styrene or a derivative thereof A block copolymer obtained by combining a block of a structural unit derived from a block of a structural unit derived from (α-substituted) acrylic acid; a block of a structural unit derived from styrene or a derivative thereof, and a siloxane or a derivative thereof A block copolymer in which a block of structural units derived from is bonded; a block of a structural unit derived from alkylene oxide and a block of structural units derived from an (α-substituted) acrylate ester Block copolymer; derived from alkylene oxide And block formation units, (alpha-substituted) and a block of a structural unit derived from acrylic acid, block copolymers such as obtained by binding.

  Examples of styrene or derivatives thereof include α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-n-octylstyrene, 2,4,6-trimethyl. Styrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-hydroxystyrene, 4-nitrostyrene, 3-nitrostyrene, 4-chlorostyrene, 4-fluorostyrene, 4-acetoxyvinylstyrene, 4-vinylbenzyl chloride 1-vinylnaphthalene, 4-vinylbiphenyl, 1-vinyl-2-pyrrolidone, 9-vinylanthracene, vinylpyridine and the like.

The (α-substituted) acrylic acid means one or both of acrylic acid or one in which a hydrogen atom bonded to a carbon atom at the α-position in acrylic acid is substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms.
Examples of (α-substituted) acrylic acid include acrylic acid and methacrylic acid.

The (α-substituted) acrylate ester means one or both of the acrylate ester or the hydrogen atom bonded to the α-position carbon atom in the acrylate ester substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms.
Examples of (α-substituted) acrylate esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, and acrylic acid. Acrylic acid esters such as hydroxyethyl, hydroxypropyl acrylate, benzyl acrylate, anthracene acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethane acrylate, propyltrimethoxysilane acrylate; methyl methacrylate, ethyl methacrylate, Propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, nonyl methacrylate, hydroxyethyl methacrylate, methacrylic acid Mud propyl, benzyl methacrylate, anthracene, glycidyl methacrylate, 3,4-epoxycyclohexyl methane, and the like methacrylic acid esters such as methacrylic acid propyl trimethoxy silane.
Among these, methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, and t-butyl methacrylate are preferable.

Examples of siloxane or derivatives thereof include dimethylsiloxane, diethylsiloxane, diphenylsiloxane, and methylphenylsiloxane.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, isopropylene oxide, butylene oxide and the like.

Among the above, as the block copolymer, a block copolymer obtained by combining a block of a structural unit derived from styrene or a derivative thereof and a block of a structural unit derived from an (α-substituted) acrylate ester; It is preferable to use a block copolymer obtained by bonding a block of a structural unit derived from the derivative and a block of a structural unit derived from (α-substituted) acrylic acid.
In the block copolymer, the proportion of structural units derived from styrene or a derivative thereof is preferably from 20 to 80 mol%, more preferably from 30 to 70 mol%, more preferably from 40 to 60, based on all the structural units constituting the block copolymer. More preferred is mol%.
In the block copolymer, the proportion of structural units derived from (α-substituted) acrylic acid or (α-substituted) acrylic ester (the proportion of the total when both are present) is the total constitutional unit constituting the block copolymer. On the other hand, 20-80 mol% is preferable, 30-70 mol% is more preferable, and 40-60 mol% is further more preferable.
A lamella oriented in a direction perpendicular to the support surface when the proportion of structural units derived from styrene or a derivative thereof, (α-substituted) acrylic acid, or (α-substituted) acrylic ester is within the above-mentioned preferred range. It is easy to obtain a phase separation structure.

Specific examples of such a block copolymer include a block copolymer having a styrene block and an acrylic acid block, a block copolymer having a styrene block and a methyl acrylate block, and a styrene block and an ethyl acrylate block. A block copolymer having a styrene block and a t-butyl acrylate block, a block copolymer having a styrene block and a methacrylic acid block, a block copolymer having a styrene block and a methyl methacrylate block, Block copolymers having styrene blocks and ethyl methacrylate blocks, block copolymers having styrene blocks and t-butyl methacrylate blocks, etc. .
In this embodiment, it is particularly preferable to use a block copolymer having a styrene block and a methyl methacrylate block.

The mass average molecular weight (Mw) of the block copolymer (polystyrene conversion standard by gel permeation chromatography) is not particularly limited as long as it is a size capable of causing phase separation, but is preferably 5000 to 100,000. 20000 to 60000 is more preferable, and 30000 to 50000 is more preferable.
The dispersity (Mw / Mn) of the block copolymer is preferably 1.0 to 3.0, more preferably 1.0 to 1.5, and still more preferably 1.0 to 1.2. In addition, Mn shows a number average molecular weight.
The period of the block copolymer (the length of one molecule of the block copolymer) is preferably 5 to 50 nm, more preferably 10 to 40 nm, and still more preferably 20 to 30 nm.

Organic solvent The organic solvent used in the block copolymer solution may be any solvent that can dissolve the block copolymer to form a uniform solution. For example, the solvent in the resin composition used as the surface treatment agent described above And the same organic solvent.

  In addition to the above block copolymer and organic solvent, the block copolymer solution may further contain an optional miscible additive, for example, an additional resin for improving the performance of the pattern made of the neutralized film 3a, a support A surfactant, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, a sensitizer, a base proliferating agent, a basic compound, and the like for improving the coating property on the body 1 are appropriately contained. be able to.

<Step (5)>
In the step (5), the layer containing the block copolymer formed in the step (4) is phase-separated.
In the present embodiment, the phase separation of the layer 4 is performed by, for example, an annealing process.
The annealing treatment may be any treatment used for phase separation of the block copolymer, such as thermal annealing or solvent annealing.
Specifically, the thermal annealing heats the support 1 on which the layer 4 is formed. The heating temperature is preferably higher than the glass transition temperature of the block copolymer to be used and lower than the thermal decomposition temperature. In the present embodiment, the heating temperature is preferably 180 to 280 ° C, and more preferably 200 to 260 ° C. The heating time is preferably 30 to 600 seconds, and more preferably 60 to 450 seconds. The heating is preferably performed in a gas having low reactivity such as nitrogen.
Solvent annealing is a method in which the support 1 on which the layer 4 is formed is annealed in a state where the support 1 is exposed to a good solvent vapor of a block copolymer. In the solvent annealing, the support 1 exposed to the good solvent vapor may be further heat-treated. Specifically, for example, the support 1 on which the layer 4 is formed is placed in a desiccator together with a good solvent for the block copolymer. Further, the support 1 on which the layer 4 is formed may be heat-treated in a state where a good solvent vapor-containing nitrogen gas obtained by bubbling nitrogen gas into a good solvent of the block copolymer is introduced.
Thus, by subjecting the layer 4 to the annealing treatment, the self-assembly of the block copolymer proceeds, the layer 4 is phase-separated into the phase 4a and the phase 4b, and has a phase-separated structure on the support 1. The structure 5 is manufactured.
In addition, the layer 4 is located on the support 1 on which a pattern made of the neutralization film 3a is formed. Then, the phase separation structure formed on the support 1 is not in a disorderly oriented state (for example, a fingerprint shape) but the orientation is controlled by the pattern made of the neutralization film 3a acting as a guide. It is formed in a state (for example, a state along a pattern made of the neutralization film 3a). Thereby, for example, a structure 5 having a lamellar or cylindrical phase separation structure oriented in a direction perpendicular to the surface of the support 1 is obtained.

<Other processes>
A fine pattern (nano-sized structure) is formed by selectively removing a phase composed of at least one block from the structure including the phase separation structure obtained in the step (5). be able to.
For example, from the structure 5, to selectively remove the phase 4a made of block P _B. Thus, only the phase 4b made P _A block remains on the support 1. That is, on the support 1, a pattern is formed only from P _A block is formed.
Specifically, in the case of using a block copolymer having a block of the block and methyl methacrylate styrene, for example by oxygen plasma treatment, consisting of methyl methacrylate block (corresponding to the block P _B) phase (the phase 4a Applicable) is selectively removed.

Selective removal process phases 4a made of block P _B is not influenced for the block P _A, if a process capable of decomposing and removing the block P _B, is not particularly limited, a dry etching method There may be a solution etching method.
The dry etching method is a method in which a reactive dry gas is sprayed on the phase separation structure and is selectively removed by the difference in the decomposition rate of the repetitive structure of the block portion with respect to the dry gas. Specific examples include oxygen plasma treatment, hydrogen plasma treatment, and ozone treatment.
In the solution etching method, if necessary, the repeating structure of a specific block region in the phase separation structure is selectively decomposed, and then the phase separation structure is immersed in a developer mainly composed of an organic solvent. In this method, a specific phase portion is preferentially dissolved and removed. In the case of solution etching method, prior to immersion in a developing solution, the layers 4 comprising a block copolymer of the support 1 after forming a phase separation structure, repetitive structures in phase 4a made of block P _B At least a part of the product is decomposed (low molecular weight). Advance by decomposing a part of the block P _B, and thus the solvency is enhanced with respect to the developing solution, phase 4a made of block P _B is likely to be selectively removed than the phase 4b consisting of P _A block.

Further, selective removal process phases 4a made of block P _B is the dry etching method is not limited to a solution etching is not particularly limited as long as the block P _B is preferentially degradable process than P _A block from among the techniques used in the degradation of the polymer can be carried out by appropriately selected depending on the type of block P _a and P _B block. For example, UV (ultraviolet) irradiation treatment, thermal decomposition treatment, chemical reaction treatment, and the like can be mentioned.

Phases is selectively removed from the structure 5, comprising a phase-separated structure (i.e., P _B of blocks phase 4a) shape and size of the component ratio or the blocks constituting the block copolymer, the block copolymer Depends on molecular weight. For example, by a relatively small component ratio per volume of the block P _B occupied in the block copolymer, can be phase 4a in the phase 4b is to form a phase separation structure present in the cylinder shape. On the other hand, by the same extent the ratio of components per volume of the block P _B and P _A block occupied in the block copolymer, the phase separation structure of the shape and the phase 4b and phase 4a are alternately stacked lamellae formed Can be made. In addition, the size of each phase can be increased by increasing the molecular weight of the block copolymer.

In this way, the support provided with a pattern formed of only P _A block produced on the surface, it can be used as a semiconductor element or the like. Further, it can be used as a template for forming a nanostructure made of metal, and by using it as a template, a metal nanostructure having a very fine shape can be formed.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.
In this example, the compound represented by the chemical formula (1) is referred to as “compound (1)”, and the same applies to compounds represented by other chemical formulas.
The photosensitive resin composition, the neutralizing film-forming surface treatment agent, and the block copolymer layer-forming resin composition used in this example are shown below.

Photosensitive resin composition 100 parts by mass of polymer compound (A1) -1, 12.18 parts by mass of compound (B) -1, 2.5 parts by mass of compound (D) -1 and 0.5% of salicylic acid Parts by mass, 1.5 parts by mass of fluorine-containing polymer compound (F) -1, 100 parts by mass of γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and cyclohexanone A photosensitive resin composition was prepared by mixing and dissolving in a mixed solvent (PGMEA: PGME: cyclohexanone = 45: 30: 25 (mass ratio)) to a solid content concentration of 2.9% by mass. .
The structures of the polymer compound (A1) -1, compound (B) -1, compound (D) -1, and fluorine-containing polymer compound (F) -1 are shown below.

With respect to the polymer compound (A1) -1, the standard polystyrene equivalent weight average molecular weight (Mw) determined by GPC measurement was 10,000, and the molecular weight dispersity (Mw / Mn) was 1.6. Moreover, the composition ratio (ratio (molar ratio) of each structural unit in the structural formula) of the polymer compound determined by ¹³ C-NMR was 1 / m = 50/50.
With respect to the fluorine-containing polymer compound (F) -1, the standard polystyrene equivalent weight average molecular weight (Mw) determined by GPC measurement was 26000, and the molecular weight dispersity (Mw / Mn) was 1.5. Moreover, the composition ratio (ratio (molar ratio) of each structural unit in the structural formula) of the polymer compound determined by ¹³ C-NMR was 1 / m = 80/20.

-Surface treatment agent for neutralization film formation As a surface treatment agent for neutralization film formation, a polymer compound represented by the following chemical formula (N) -1 is dissolved in propylene glycol monomethyl ether acetate (PGMEA). By doing this, a resin composition (2 mass% PGMEA solution) was prepared.
With respect to the polymer compound (N) -1, the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 40000, and the molecular weight dispersity (Mw / Mn) was 1.6. Moreover, the composition ratio (ratio (molar ratio) of each structural unit in the structural formula) of the polymer compound determined by ¹³ C-NMR was l / m / n = 25/70/5.

-Resin composition for block copolymer layer formation (block copolymer solution)
A block copolymer (PS-b-PMMA) of a block consisting of repeating units of styrene and a block consisting of repeating units of methyl methacrylate is dissolved in PGMEA to obtain a resin composition (solid content concentration of the block copolymer of 0. 4 mass% PGMEA solution) was prepared.
Regarding the block copolymer (PS-b-PMMA), the proportion of styrene repeating units is 50 mol% and the proportion of methyl methacrylate repeating units is 50 mol% with respect to all the structural units constituting the block copolymer; The weight average molecular weight (Mw) was 40000, and the dispersity (Mw / Mn) was 1.04.

≪Pattern formation≫
Using the photosensitive resin composition and the surface treatment agent for forming a neutralized film, a pattern comprising a neutralized film is formed on the support (silicon wafer on which an organic antireflection film is formed) as follows. Thus formed.

Example 1
Step (1):
An organic antireflection film composition “ARC29” (trade name, manufactured by Brewer Science Co., Ltd.) is applied onto an 8-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds to be dried. Thus, an organic antireflection film having a film thickness of 82 nm was formed.
Next, the photosensitive resin composition is applied onto the organic antireflection film using a spinner, prebaked (PAB) at a temperature of 110 ° C. for 60 seconds on a hot plate, and then dried. As a result, a photosensitive resin film having a thickness of 150 nm was formed.
Next, an ArF excimer laser (193 nm) was applied to the photosensitive resin film by an exposure apparatus NSR-S302B (manufactured by Nikon; NA (numerical aperture) /s=0.60/ (2/3 Ann.)) As a mask pattern. Selectively irradiated via (6% halftone).
Subsequently, a post-exposure heating (PEB) treatment was performed at a temperature of 90 ° C. for 60 seconds, followed by negative development with butyl acetate at 23 ° C. for 20 seconds, followed by shake-off drying.
Thereafter, baking was performed at 200 ° C. for 300 seconds (200 ° C. baking).
As a result, a 1: 1 line and space prepattern (hereinafter also referred to as “LS prepattern”) having a line width of 160 nm and a pitch of 320 nm was formed.

Step (2):
Next, the surface treatment agent for forming the neutralization film is spin-coated on the organic antireflection film on which the LS prepattern is formed so as to cover the LS prepattern (rotation number: 1500 rpm, 60 seconds) And a neutralized film having a thickness of 10 nm was formed on the LS prepattern and on the organic antireflection film by baking at 200 ° C. for 300 seconds and drying.

Step (3):
Next, the LS pre-pattern and the neutralized film formed on the organic antireflection film were converted to a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution “NMD-3” at 23 ° C. Alkali development was performed for 60 seconds using a trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd. As a result, the LS prepattern was removed.
Thereafter, baking was performed at 100 ° C. for 60 seconds and drying was performed.

  And when the surface of the support after the drying was observed using a scanning electron microscope (acceleration voltage 800V, trade name: SU8000, manufactured by Hitachi High-Technologies Corporation), the support had a space width of 160 nm and a pitch of 320 nm. A pattern consisting of a neutralized film of 1: 1 space and line was confirmed.

(Example 2)
Step (1) is performed in the same manner as in Example 1 except that the 200 ° C. baking after the negative development in Step (1) in Example 1 is changed to 180 ° C. baking (baking at 180 ° C. for 300 seconds). , (2) and (3) were performed.
And when the surface of the support after the drying was observed using a scanning electron microscope (acceleration voltage 800V, trade name: SU8000, manufactured by Hitachi High-Technologies Corporation), the support had a space width of 160 nm and a pitch of 320 nm. A pattern consisting of a neutralized film of 1: 1 space and line was confirmed.

(Example 3)
The polymer compound (A1) -1 blended in the photosensitive resin composition used in Example 1 is a polymer compound having a mass average molecular weight (Mw) of 5000 (structure, composition ratio and molecular weight dispersity are high. Steps (1), (2), and (3) were carried out in the same manner as in Example 1 except that the molecular compound (A1) -1 was changed).
And when the surface of the support after the drying was observed using a scanning electron microscope (acceleration voltage 800V, trade name: SU8000, manufactured by Hitachi High-Technologies Corporation), the support had a space width of 160 nm and a pitch of 320 nm. A pattern consisting of a neutralized film of 1: 1 space and line was confirmed.

Example 4
The polymer compound (A1) -1 blended in the photosensitive resin composition used in Example 1 is a polymer compound having a mass average molecular weight (Mw) of 50000 (structure, composition ratio and molecular weight dispersity are high. Steps (1), (2), and (3) were carried out in the same manner as in Example 1 except that the molecular compound (A1) -1 was changed).
And when the surface of the support after the drying was observed using a scanning electron microscope (acceleration voltage 800V, trade name: SU8000, manufactured by Hitachi High-Technologies Corporation), the support had a space width of 160 nm and a pitch of 320 nm. A pattern consisting of a neutralized film of 1: 1 space and line was confirmed.

  From the above, according to the pattern forming methods of Examples 1 to 4, the guide pattern can be formed by a simple method without requiring exposure and baking operations to peel off the etching and LS prepattern. I understand.

≪Manufacture of structure including phase separation structure≫
Using the resin composition for forming the block copolymer layer, a phase separation structure was produced as follows on the support on which the pattern comprising the neutralized film was formed.
(Example 5)
Step (4):
The resin composition for forming the block copolymer layer is spin-coated on the support on which the pattern comprising the neutralized film obtained in Example 1 is formed so as to cover the pattern (rotation speed: 1500 rpm, 60 Second) to form a 30 nm thick block copolymer layer.
Step (5):
The support on which the block copolymer layer was formed was thermally annealed by heating at 250 ° C. for 1 minute.

  Then, the surface of the support after the thermal annealing was observed using a scanning electron microscope (acceleration voltage 800 V, trade name: SU8000, manufactured by Hitachi High-Technologies Corporation). It was confirmed that a structure having a lamellar phase separation structure (period = 26 nm) aligned in parallel and perpendicular to the support surface was produced.

DESCRIPTION OF SYMBOLS 1 Support body 2 Photosensitive resin film 3 Neutralization film 4 Layer 5 Structure

Claims (6)

A photosensitive resin film is formed on a support using a photosensitive resin composition that generates an acid upon exposure and changes in solubility in a developer due to the action of the acid, and exposes the photosensitive resin film, A step (1) of forming a pre-pattern by negatively developing the exposed photosensitive resin film with a developer containing an organic solvent;
A step (2) of forming a neutralized film containing a surface treatment agent on the support on which the pre-pattern is formed;
The pre-pattern and the neutralized film formed on the support are alkali-developed, the pre-pattern is removed from the support, and a pattern comprising the neutralized film is formed on the support. Step (3) to perform,
A pattern forming method comprising:   The pattern forming method according to claim 1, wherein baking is performed at 180 ° C. or higher after the negative development in the step (1).   The pattern formation method of Claim 1 or 2 in which the said photosensitive resin composition contains the base material component (A) from which the solubility with respect to the said organic solvent reduces by the effect | action of an acid.   The pattern formation method of Claim 3 in which the said base material component (A) contains the high molecular compound (A1) which has the structural unit (a1) containing the acid-decomposable group which polarity increases by the effect | action of an acid.   The pattern formation method of Claim 4 whose mass mean molecular weights of the said high molecular compound (A1) are 5000-50000. A block in which a plurality of types of polymers are bonded to a support on which a pattern made of the neutralized film is formed by the pattern forming method according to any one of claims 1 to 5 so as to cover the pattern. Forming a layer comprising a copolymer (4);
(5) separating the layer containing the block copolymer;
The manufacturing method of the structure containing a phase-separation structure characterized by including this.

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