TWI545403B - Pattern forming method, pattern, resin composition, film, blank A method for manufacturing a mask, a mask, a mask, a method for manufacturing a die for nanoimprinting, and a die for nanoimprinting - Google Patents

Description

Pattern forming method, pattern, resin composition, film, blank Mask, mask manufacturing method, mask, method for manufacturing nano imprinting mold, and mold for nano imprinting

The present invention relates to an ultramicrolithography process or other photofabrication which can be preferably used in the manufacture of a large scale integrated circuit (LSI) or a high capacity microchip. A pattern forming method, a pattern, a sensitized ray-sensitive or radiation-sensitive resin composition, and a photosensitive method capable of forming a high-definition pattern using an electron beam (Electron Beam, EB) or Extreme Ultraviolet (EUV) Radiation-sensitive or radiation-sensitive linear films, and mask blanks with sensitizing ray-sensitive or radio-sensitive linear films.

Further, the pattern forming method of the present invention can be preferably applied to a method of manufacturing a photomask or a method of manufacturing a mold for nanoimprinting. The present invention also relates to a method for producing a photomask, a photomask, a method for producing a nanoimprint mold, and a mold for nanoimprint.

In the microfabrication using the resist composition, in recent years, with the high integration of the integrated circuit, it has been demanded in recent years to form an ultrafine (for example, a line and space of 1:1 line width of 25 nm or less) pattern.

Therefore, the exposure wavelength also tends to be shorter than that of the x-ray to the i-ray and the excimer laser light. Currently, development of a lithography technique using extreme ultraviolet light (EUV) or electron beam is being promoted. Moreover, in recent years, it has been used for mold making applications and the like used in the so-called imprint process (for example, Patent Document 1).

Further, with the miniaturization of the formed pattern, it becomes more difficult to control the line width, and the line width uniformity (Critical Dimension Uniformity; hereinafter abbreviated as CDU) in the wafer surface is deteriorated. problem. Although the improvement of the resist is performed in order to prevent this problem, it is not sufficient, and there is a concern that the yield at the time of manufacturing an integrated circuit deteriorates. Further, with the miniaturization of the line width, it is difficult to suppress the line width variation (also referred to as exposure latitude), which is referred to as EL (Exposure Latitude), with respect to the exposure amount, and improvement is required.

As a lithography technique using an extreme ultraviolet light (EUV) or an electron beam, and a resist composition used in the production of a mold for imprinting, for example, an acid-labile group such as an acetal structure is used for a phenolic hydroxyl group. A resin in which a hydrogen atom has been substituted is disclosed, for example, in Patent Document 2 to Patent Document 4.

As an alkaline developing solution used in the positive-type chemically amplified image forming method, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter abbreviated as TMAH aqueous solution) has been used as a practical industrial standard developing solution, but With the miniaturization of the pattern as described above, the line edge roughness (LER) due to the thinning of the film of the resist film during development becomes a problem.

In order to solve this problem, for example, the following method has been proposed: when developing a positive novolak resist, an alkaline developer solution of 0.115 N to 0.15 N is used. A method of developing a pattern (for example, Patent Document 5); or a method of developing a resist film formed of the following resist composition using an aqueous solution of TMAH of 1.2% by mass or less (for example, Patent Document 6): The resist composition contains a resin having an acid-decomposable repeating unit of an ester type; and a method of developing a resist film formed of the following resist composition using a 0.5% by mass to 1.1% by mass aqueous solution of TMAH (for example, Patent Document 7): The resist composition contains a resin having a repeating unit in which a hydrogen atom of a phenolic hydroxyl group is substituted with an acid leaving group.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-162101

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-239538

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-146242

[Patent Document 4] International Publication No. 05/023880

[Patent Document 5] Japanese Patent Laid-Open Publication No. SHO 63-232430

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-134240

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2013-44809

However, the current situation is that the line width uniformity (CDU), the exposure latitude (EL), and the goodness of the ultrafine pattern cannot be satisfied in all combinations of the existing resist composition, developer, eluent, and the like. Line edge roughness (LER).

An object of the present invention is to provide a pattern forming method, a pattern, and a photosensitive method. a radiation-sensitive or radiation-sensitive linear resin composition, a sensitizing ray-sensitive or radiation-sensitive film, and a blank mask having a sensitizing ray-sensitive or radiation-sensitive film, the pattern forming method providing an exposure latitude (EL An ultrafine pattern having a large line edge roughness (LER) and a good line width uniformity (CDU), for example, a line width of 25 nm or less.

Further, an object of the present invention is to provide a method for producing a photomask including the pattern forming method, a method for producing a nanoimprint mold, a photomask, and a mold for nanoimprint.

As a result of intensive studies, the present inventors have found that pattern exposure is performed on a sensitized ray-sensitive or radiation-sensitive film formed by using a sensitizing ray-sensitive or radiation-sensitive resin composition containing a polymer compound having a specific structure. Thereafter, development is carried out using an alkaline developing solution having a specific alkaline component concentration, whereby the object can be attained.

That is, the present invention is as follows in one aspect.

[1] A pattern forming method comprising: - a step of applying a sensitizing ray-sensitive or radiation-sensitive resin composition onto a substrate to form a sensitized ray-sensitive or radiation-sensitive film; - the sensitizing ray property Or a step of exposing the radiation sensitive film; and a step of developing the exposed sensitizing ray-sensitive or radiation-sensitive film using an alkali developing solution, wherein the sensitizing ray-sensitive or radiation-sensitive resin The composition contains (A) a polymer compound containing a repeating unit represented by the following formula (I), and the concentration of the alkaline component in the alkaline developing solution is 1.25 to 2.2% by mass.

In the formula (I), R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; R ₀₃ may be bonded to Ar ₁ to form Ring, where R ₀₃ represents an alkylene group; Ar ₁ represents an (n+1)-valent aromatic ring group, and when bonded to R ₀₃ to form a ring, represents an (n+2)-valent aromatic ring group; Each of Y represents independently a hydrogen atom or a group which is desorbed by the action of an acid; wherein at least one of Y represents a group which is desorbed by the action of an acid; and n represents an integer of 1 to 5.

[2] The pattern forming method according to [1], wherein the alkaline developing solution is an aqueous solution containing tetramethylammonium hydroxide.

[3] The pattern forming method according to [1] or [2], wherein the alkaline developing solution contains an alcohol.

[4] The pattern forming method according to any one of [1] to [3] wherein The alkaline developer contains a surfactant.

[5] The pattern forming method according to any one of [1] to [4] wherein the exposure in the exposing step is performed by electron beam or extreme ultraviolet light.

[6] The pattern forming method according to any one of [1] to [5] wherein, in the formula (I), at least one Y is a group represented by the following formula (II),

Wherein L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; M represents a single bond or a divalent linking group; and Q represents an alkyl group, a cycloalkyl group, or an aromatic group; a group, an amine group, an ammonium group, a thiol group, a cyano group or an aldehyde group; the cycloalkyl group and the aryl group may contain a hetero atom; at least two of Q, M, and L ₁ may be bonded to each other to form a ring.

[7] The pattern forming method according to [6], wherein the atom adjacent to the carbon atom in the formula of at least one of L ₁ and L ₂ in the formula (II) is a tertiary carbon atom or a quaternary carbon atom.

[8] The pattern forming method according to any one of [1] to [7] wherein, in the formula (I), at least one Y is a group represented by the following formula (III),

Wherein L ₃ , L ₄ and L ₅ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; wherein, L ₃ , L ₄ and L ₅ are not all hydrogen atoms; The cycloalkyl group and the aryl group may contain a hetero atom; at least two of L ₃ , L ₄ and L ₅ may be bonded to each other to form a ring.

[9] The pattern forming method according to any one of [1] to [8] wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains (B) irradiation by actinic rays or radiation An acid-producing compound.

[10] A pattern formed by the pattern forming method according to any one of [1] to [9].

[11] A sensitizing ray-sensitive or radiation-sensitive resin composition for use in the pattern forming method according to any one of [1] to [9].

[12] A photosensitive ray-sensitive or radiation-sensitive film formed using the sensitized ray-sensitive or radiation-sensitive resin composition according to [11].

[13] A blank mask comprising the sensitized ray-sensitive or radiation-sensitive film according to [12].

[14] A method of manufacturing a photomask, comprising the method of any one of [1] to [9] The pattern forming method described.

[15] A photomask manufactured by the method of manufacturing a photomask according to [14].

[16] A method of producing a mold for a nanoimprint, which comprises the pattern forming method according to any one of [1] to [9].

[17] A mold for nanoimprinting, which is produced by the method for producing a mold for nanoimprint according to [16].

According to the present invention, there is provided a pattern forming method, a method of manufacturing a photomask including the pattern forming method, and a method of manufacturing a nanoimprinting mold, wherein the pattern forming method can form a comprehensively good EL, LER, and CDU. An ultrafine pattern having a line width of 25 nm or less which is excellent in developability and productivity. Further, according to the present invention, it is possible to provide a photosensitive ray- or radiation-sensitive resin composition, a sensitizing ray-sensitive or radiation-sensitive film which can be preferably used in the pattern forming method, and to have a sensitizing ray property or a feeling A blank mask for the radioactive film.

Hereinafter, embodiments for carrying out the invention will be described in detail.

Specifically, the method of forming a resist pattern of the present invention will be described in detail.

Further, in the expression of the group (atomic group) in the present specification, the unsubstituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and Containing a substituent group (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present invention, the term "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far-ultraviolet light represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like. Further, in the present invention, "light" means actinic rays or radiation.

The term "exposure" as used in the present specification refers to exposure by a mercury lamp, a far-ultraviolet light represented by a pseudo-molecular laser, X-rays, EUV light, or the like, and an electron beam, an ion beam, etc., unless otherwise specified. The depiction of the particle beam is also included in the exposure.

[Pattern forming method]

The pattern forming method of the present invention comprises: a step of applying a sensitizing ray-sensitive or radiation-sensitive resin composition onto a substrate to form a sensitized ray-sensitive or radiation-sensitive film (film forming step); a step of exposing the ray-sensitive or radiation-sensitive film; and - developing the exposed sensitizing ray-sensitive or radiation-sensitive film using an alkaline developing solution.

One of the features of the pattern forming method of the present invention is that a sensitized ray containing a polymer compound having a repeating unit represented by the above formula (I) is used as the sensitized ray-sensitive or radiation-sensitive resin composition. Or a radiation-sensitive linear resin composition, and as the alkaline developing solution, the concentration of the alkaline component is 1.25 An alkaline developer having a mass % to 2.2% by mass.

The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a chemically amplified sensitized ray-sensitive or radiation-sensitive resin composition.

Further, the resist pattern of the present invention is formed by the pattern forming method of the present invention.

Further, as described later, the present invention also relates to a sensitized ray-sensitive or radiation-sensitive resin composition for use in the resist pattern forming method of the present invention (hereinafter also referred to as "the composition of the present invention" "Wait).

Hereinafter, the method of forming a resist pattern of the present invention will be described in detail.

<film forming step>

In the film forming step of forming the sensitizing ray-sensitive or radiation-sensitive film, the sensitizing ray-sensitive or radiation-sensitive resin composition is subjected to filter filtration as needed, and then applied onto a support (substrate). The filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less.

As a method of applying a sensitizing ray-sensitive or radiation-sensitive resin composition to a support (substrate), an appropriate coating method such as a spinner can be used. As the substrate, a substrate (for example, tantalum or ruthenium dioxide coated) which is used in the production of an integrated circuit element can be used. If necessary, various base films (inorganic films, organic films) may be applied between the sensitizing ray-sensitive or radiation-sensitive film and the substrate.

In the present invention, in order to analyze an ultrafine pattern such as a line and a space pattern having a line width of 25 nm or less, it is preferably sensitized ray or radiation. The film thickness of the linear film is 60 nm or less. By setting the film thickness to 60 nm or less, the aspect ratio of the pattern becomes small, and it is difficult to cause pattern collapse. The range of the film thickness is preferably 15 nm to 60 nm. When the film thickness is 15 nm or more, good etching resistance can be obtained, which is preferable. The range of the film thickness is more preferably 15 nm to 50 nm, particularly preferably 15 nm to 40 nm. When the film thickness is in this range, excellent etching resistance and analytical performance can be simultaneously satisfied.

<Exposure step>

The actinic radiation or radiation sensitive film formed is irradiated with actinic rays or radiation through a predetermined mask. Furthermore, the illumination of the electron beam is generally a depiction (direct depiction) that does not intervene in the mask.

The actinic ray or the radiation is not particularly limited, and examples thereof include a KrF excimer laser, an ArF excimer laser, an EUV light, an electron beam, and the like, and are preferably EUV light or electron beam.

<baking step>

The pattern forming method of the present invention may also include a baking (heating) step, and may also include a plurality of baking steps.

In one aspect of the pattern forming method of the present invention, it is preferred to include a baking (referred to as "prebake", hereinafter abbreviated as "PB") step after film formation and before exposure. The PB temperature is preferably from 60 ° C to 150 ° C, more preferably from 80 ° C to 140 ° C. The PB time is preferably from 60 seconds to 1200 seconds, more preferably from 60 seconds to 600 seconds.

PB can take advantage of the usual exposure. The mechanism provided in the developing machine may be carried out, or may be performed using a heating plate or the like.

In another aspect of the pattern forming method of the present invention, it is preferred to include baking (referred to as Post Exposure Bake, hereinafter abbreviated as "PEB") after exposure and before development.

The PEB temperature is preferably from 80 ° C to 150 ° C, more preferably from 90 ° C to 150 ° C, and further preferably from 100 ° C to 140 ° C.

The PEB time is preferably from 30 seconds to 1000 seconds, more preferably from 60 seconds to 800 seconds, and preferably from 60 seconds to 600 seconds.

PEB can take advantage of the usual exposure. The unit provided in the developing machine may be carried out, or may be performed using a heating plate or the like.

The reaction of the exposed portion is promoted by PEB, and the CDU and LER are improved.

<alkali development step>

The concentration of the alkaline component of the alkaline developer is from 1.25 mass% to 2.2 mass% with respect to the total mass of the alkaline developer. By setting the concentration of the alkaline component to the above range, the CDU is increased. The reason is not clear, but it is considered that by setting the concentration of the alkaline component to the above range, it is possible to suppress the alkali component from being deactivated by carbon dioxide in the atmosphere and the component concentration locally fluctuating in the wafer surface. The influence of the variation in the line width in the plane can simultaneously suppress the variation in line width caused by the thinning of the film in the unexposed portion of the resist film.

In addition, when the concentration of the alkaline component is in the above range and a sensitizing ray-sensitive or radiation-sensitive resin composition containing a polymer compound having a repeating unit represented by the above formula (I) is used, the CDU is improved. At the same time, LER and EL are improved, and the resolution performance is improved. The reason is not clear, but it can be considered: by alkaline The combination of the concentration of the alkaline component in the developer and the polymer compound can suppress the thinning of the film in the unexposed portion of the sensitizing ray or the radiation sensitive film, thereby suppressing the edge roughness caused by the film roughening at the edge of the pattern. In addition, variation in line width due to a decrease in film thickness due to film thinning can be suppressed, and as a result, variation in line width with respect to change in exposure amount can be suppressed, and EL can be improved.

In one aspect of the invention, the concentration of the alkaline component in the alkaline developer is preferably 1.25 mass% to 2.0 mass%, more preferably 1.35 mass% to 1.8 mass%.

Examples of the alkaline component (hereinafter also referred to as "basic species") in the alkaline developing solution to be used include inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia. Bases, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine, etc. Alcoholamines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctyl hydroxide Tetraalkylammonium hydroxide such as ammonium, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide or dibutyldipentylammonium hydroxide, trimethylbenzene A basic ammonium salt such as ammonium hydroxide, trimethylbenzylammonium hydroxide or triethylbenzylammonium hydroxide, or a basic amine such as a cyclic amine such as pyrrole or piperidine, which can be used as an alkaline developer. An aqueous solution of these basic species.

Further, an appropriate amount of an alcohol such as isopropanol or a surfactant such as a nonionic surfactant may be added to the aqueous solution of the base (for example, Sophino 440, Sophino 465 (Japan Chemical Industry Co., Ltd.) )) An alkaline aqueous solution which lowers the surface tension. By lowering the surface tension, the wettability of the developer to the wafer is improved, and the CDU is improved.

The surfactant such as an alcohol or a nonionic surfactant may be added in an amount necessary to sufficiently reduce the surface tension of the alkaline developer.

The relationship between the amount of the alcohol or the surfactant added and the surface tension of the aqueous solution varies depending on the kind of the compound to be added, so the amount of addition cannot be generalized, for example, when the isopropanol is added, the total mass relative to the alkaline developer By adding 5% by mass to 20% by mass, the surface tension of the alkaline developing solution can be lowered to 30 mN/m to 50 mN/m.

The surface tension can be measured by a known method, for example, a CBVP-Z type manufactured by Kyowa Interface Science Co., Ltd., and an assay using a platinum plate.

Among the alkaline species in the developing solution, a quaternary ammonium salt is preferred, and tetramethylammonium hydroxide is further preferred.

Further, it is preferable that the alkaline developing solution does not contain metal ions and halogen ions, and it is preferable that the metal ions and the halogen ions are 0 mass ppb, respectively, but it is not excluded that it does not impair the effects of the present invention. A small amount of situation. The content of the metal ions in the developer is preferably 10 mass ppb or less, and the halogen ion content is preferably 10 mass ppb or less.

As a developing method, for example, a method of immersing a substrate in a tank filled with a developing solution for a fixed period of time (dipping method), and a method of developing by depositing a developing solution on the surface of the substrate by a surface tension and stationary for a fixed period of time can be applied. Puddle method; a method of spraying a developer onto a surface of a substrate (spray method); a method of continuously ejecting a developer onto a substrate rotating at a fixed speed while scanning a developer discharge nozzle at a fixed speed (dynamic dispensing) Method, spray development method, etc.

Further, after the step of developing, the step of stopping the development while replacing the other solvent may be carried out.

A particularly preferred development method is a method of continuously supplying a substantially fresh alkaline developer for development, specifically, a method of continuously spraying a substantially fresh alkaline developer onto the surface of a substrate (spray method), or A method of continuously ejecting a substantially fresh alkaline developing solution onto a substrate rotating at a fixed speed while scanning a developing solution discharge nozzle at a fixed speed (dynamic dispensing method). The development is carried out by continuously supplying a substantially fresh alkaline developing solution, and the development of the exposed portion is promptly performed, and the analytical performance is improved. Further, by continuously supplying a fresh alkaline developing solution and then performing development, it is possible to reduce development defects of the residue system which occurs in the stage of switching from auto development to rinsing.

Regarding the development time, it is important to take into consideration both the sensitizing ray property of the exposed portion or the time and productivity in which the components in the radiation-sensitive resin composition are sufficiently dissolved. The development time varies depending on the concentration of the alkaline species contained in the developer and the alkali solubility of the components in the sensitizing ray or the radiation-sensitive resin composition, and thus cannot be uniformly determined.

The temperature of the developer is preferably from 0 ° C to 50 ° C, and more preferably from 10 ° C to 30 ° C.

<rinsing step>

In one aspect of the pattern forming method of the present invention, it is preferred to include a rinsing step of stopping the development while replacing the pure water with the step of performing the development.

In the rinsing step, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a nonionic surfactant may be added to the pure water.

The rinsing time is preferably a time for sufficiently rinsing the alkaline developing solution on the substrate, and is usually preferably from 5 seconds to 600 seconds. And then preferably 10 seconds to 300 seconds.

The temperature of the eluent is preferably from 0 ° C to 50 ° C, and more preferably from 10 ° C to 30 ° C.

Further, the present invention relates to a mold for nanoimprint manufactured by a method for producing a mold for nanoimprint comprising the pattern forming method of the present invention, and a light comprising the pattern forming method of the present invention. A photomask manufactured by a method of manufacturing a cover.

Such a nanoimprint mold and a photomask are preferably produced by using a blank mask having a sensitizing ray or a feeling obtained from the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention. Radiation linear film.

When a pattern is formed by the pattern forming method of the present invention on such a blank mask having a sensitizing ray-sensitive or radiation-sensitive film, a transparent substrate such as quartz or calcium fluoride may be used as the substrate to be used. In general, it is necessary to laminate a light shielding film, an antireflection film, and a functional film such as a phase transfer film, an additional etching stopper film, or an etching mask on the substrate. As a material of the functional film, a film containing ruthenium or a transition metal such as chromium, molybdenum, zirconium, hafnium, tungsten, titanium or tantalum is laminated. In addition, as a material used in the outermost layer, a material containing cerium or a material containing oxygen and/or nitrogen in cerium as a main constituent material, and a material containing a transition metal in the material as a main component may be exemplified. a ruthenium compound material of a material; or a transition metal, particularly one or more selected from the group consisting of chromium, molybdenum, zirconium, hafnium, tungsten, titanium, hafnium, etc., or further comprising one or more selected from the group consisting of oxygen and nitrogen The material of the element in carbon is a transition metal compound material mainly composed of a material.

The light shielding film may be a single layer, but more preferably a multilayer structure in which a plurality of materials are overlapped and coated. In the case of a multilayer structure, the thickness of the film of each layer is not particularly limited, and is preferably 5 nm to 100 nm, more preferably 10 nm to 80 nm. The thickness of the entire light-shielding film is not particularly limited, but is preferably 5 nm to 200 nm, more preferably 10 nm to 150 nm.

Next, the sensitizing ray-sensitive or radiation-sensitive film is exposed and developed as described above to obtain a pattern. Then, the pattern is used as a mask to appropriately perform an etching treatment or the like to produce a mold for a nanoimprint or a photomask.

The photomask in the present invention may be a light-transmitting type mask used in an ArF excimer laser or the like, or may be a light-reflecting type mask used in a reflection-based lithography using EUV light as a light source.

In addition, a process for producing a mold for a nanoimprint using the composition of the present invention is disclosed, for example, in Japanese Patent No. 4109085, Japanese Patent Laid-Open No. 2008-162101, and "Basic and Technology of Nano Imprinting". Development. Application development - Nano-imprinted substrate technology and the latest technology development - Edit: Hirai Yoshihiko (Frontier published).

The pattern forming method of the present invention can also be used for guiding pattern formation in Directed Self-Assembly (DSA) (for example, refer to "ACS Nano" Vol. 4 No. 8 page 4815 - page 4823).

Further, the pattern formed by the above-described method can be used, for example, as a core material (core) of a spacer process disclosed in Japanese Laid-Open Patent Publication No. Hei-3-270227 and Japanese Patent Laid-Open No. Hei No. 2013-164509.

[Photosensitive ray-sensitive or radiation-sensitive resin composition]

Hereinafter, the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention used in the pattern forming method of the present invention will be described in detail.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a polymer compound having a repeating unit represented by the above formula (I).

The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a compound which generates an acid by irradiation with actinic rays or radiation, and a basic compound.

[1] Polymer compound

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a polymer compound having a repeating unit represented by the following formula (I) (hereinafter referred to as "polymer compound (A)"). When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray or high-energy light having a wavelength of 50 nm or less (for example, EUV), the polymer compound (A) preferably has a hydroxystyrene repeating unit. . Here, as the hydroxystyrene, p-hydroxystyrene is preferred.

The polymer compound having a repeating unit represented by the formula (I) can be synthesized by using a monodisperse polymer synthesized by an anionic polymerization method or the like as a precursor as described later. When the ultrafine pattern is formed by the present invention, by using a monodisperse polymer, the dissolution unit at the time of development becomes uniform, and excellent resolution, particularly small line edge roughness (LER), can be achieved.

[Chemical 4]

In the formula (I), R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₀₃ may be bonded to Ar ₁ to form a ring, and R _{03 in this case} represents an alkylene group.

Ar ₁ represents an (n+1)-valent aromatic ring group, and when bonded to R ₀₃ to form a ring, represents an (n+2)-valent aromatic ring group.

Each of n Y independently represents a hydrogen atom or a group which is desorbed by the action of an acid. Wherein at least one of Y represents a group which is detached by the action of an acid.

n represents an integer of 1 to 5, preferably 1 or 2, more preferably 1.

The alkyl group as R ₀₁ to R ₀₃ is, for example, an alkyl group having a carbon number of 20 or less, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a hexyl group or a 2-ethyl group. Hexyl, octyl or dodecyl. More preferably, the alkyl group is an alkyl group having 8 or less carbon atoms. Further, the alkyl groups may have a substituent.

The alkyl group contained in the alkoxycarbonyl group is preferably the same alkyl group as the alkyl group in the above R ₀₁ to R ₀₃ .

The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Preferable examples thereof include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Further, the cycloalkyl groups may have a substituent.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom.

When R ₀₃ represents an alkylene group, as the alkylene group, a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group and a decyl group are preferably alkyl groups having 1 to 8 carbon atoms. .

R ₀₁ , R ₀₂ and R ₀₃ preferably each independently represent a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

The (n+1)-valent aromatic ring group of Ar ₁ is preferably a carbon number of 6 to 14. Examples of the divalent aromatic ring group when n is 1 include a stretching phenyl group, a methylphenyl group, and a stretching naphthyl group.

Specific examples of the (n+1)-valent aromatic ring group when n is an integer of 2 or more include (n-1) arbitrary examples of the specific examples of the divalent aromatic ring group. A group of hydrogen atoms.

Further, the aromatic ring groups may further have a substituent.

As a result of the action of an acid from the group of Y, include, for example, by a _{-C (R 36) (R 37} ) (R 38), - C (= O) -OC (R 36) (R 37) (R 38) , -C(R ₁ )(R ₂ )(OR ₃₉ ), -C(R ₁ )(R ₂ )-C(=O)-OC(R ₃₆ )(R ₃₇ )(R ₃₈ ), and -CH (R ₃₆ ) (Ar) represents a group.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring structure.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group.

Ar represents an aryl group.

The alkyl group as R ₃₆ to R ₃₉ , R ₁ or R ₂ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group and a hexyl group. And Xinji.

The cycloalkyl group as R ₃₆ to R ₃₉ , R ₁ or R ₂ may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a fluorenyl group, a dicyclopentyl group, and an α-nonenyl group ( Α-pinenyl), tricyclodecyl, tetracyclododecyl and androstanyl. Further, a part of the carbon atoms in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

The aryl group of R ₃₆ to R ₃₉ , R ₁ , R ₂ or Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group and an anthracenyl group.

As _{R 36 ~ R 39, R 1} , or R ₂ is preferably an aralkyl group having a carbon number of aralkyl group having 7 to 12, for example, preferably a benzyl group, phenethyl group and naphthylmethyl.

The alkenyl group of R ₃₆ to R ₃₉ , R ₁ or R ₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group.

The ring formed by bonding R ₃₆ and R _{37 to} each other may be a single ring type or a polycyclic type. The monocyclic type is preferably a cycloalkane structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. The polycyclic type is preferably a cycloalkane structure having 6 to 20 carbon atoms, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. Further, a part of the carbon atoms in the ring structure may be substituted by a hetero atom such as an oxygen atom.

Each of the groups may have a substituent. As the substituent, for example, an alkane can be mentioned Base, cycloalkyl, aryl, amine, decyl, ureido, urethane, hydroxy, carboxy, halogen, alkoxy, thioether, decyl, decyloxy, alkoxy Alkylcarbonyl, cyano and nitro. These substituents preferably have a carbon number of 8 or less.

The group Y which is detached by the action of an acid is more preferably a structure represented by the following formula (II).

In the formula (II), L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group, an aryl group, an amine group, an ammonium group, a thiol group, a cyano group or an aldehyde group. Furthermore, the cycloalkyl and aryl groups may contain heteroatoms.

Furthermore, at least two of Q, M and L ₁ may be bonded to each other to form a ring.

The alkyl group as L ₁ and L _{2 is} , for example, an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a hexyl group, and an octyl group.

The cycloalkyl group as L ₁ and L _{2 is} , for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group, and an anthracenyl group.

The aralkyl group as L ₁ and L _{2 is} , for example, an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include a benzyl group and a phenethyl group.

L ₁ and L ₂ preferably each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group. More preferably, L ₁ is a hydrogen atom. More preferably, L ₂ is an alkyl group or a cycloalkyl group, and further preferably, in the alkyl group and the cycloalkyl group, the atom adjacent to the carbon atom in the formula (II) is a tertiary carbon atom or a quaternary carbon atom. Good for a four-stage carbon atom.

The divalent linking group as M is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethyl group, a propyl group, a butyl group, a hexyl group or a decyl group). a cycloalkyl group (preferably a cycloalkyl group having a carbon number of 3 to 15, such as a cyclopentyl group or a cyclohexyl group), an alkenyl group (preferably an alkenyl group having 2 to 8 carbon atoms, for example) a vinyl group, a propylene group or a butenyl group, an aryl group (preferably a aryl group having a carbon number of 6 to 20, such as a phenyl group, a methylphenyl group or a naphthyl group), -S-, -O-, -CO-, -SO ₂ -, -N(R ₀ )-, or a combination of two or more of these. Here, R ₀ is a hydrogen atom or an alkyl group. The alkyl group as R _{0 is} , for example, an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a hexyl group, and an octyl group.

M preferably represents a single bond, or an alkyl group, -O-, or a divalent linking group comprising a combination of these, more preferably a single bond, an alkylene group or an alkyleneoxy group.

The alkyl group and the cycloalkyl group as Q are the same as the respective groups as L ₁ and L ₂ .

Examples of the aryl group of Q include the above-mentioned aryl groups as L ₁ and L ₂ . The cycloalkyl group and the aryl group are preferably a group having 3 to 15 carbon atoms.

Examples of the cycloalkyl group or the aryl group containing a hetero atom of Q include, for example, an episulfide group. Thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and A group having a heterocyclic structure such as pyrrolidone. However, as long as it is a ring formed of carbon and a hetero atom or a ring formed only of a hetero atom, it is not limited to these groups.

Q preferably represents an alkyl group, a cycloalkyl group or an aryl group.

Examples of the ring structure which can be formed by bonding at least two of Q, M and L ₁ to each other include a 5-membered or 6-membered ring structure in which the propyl group or the butyl group is formed. Furthermore, the 5- or 6-membered ring structure contains oxygen atoms.

Each group represented by L ₁ , L ₂ , M and Q in the formula (II) may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, and a thioether group. Mercapto, decyloxy, alkoxycarbonyl, cyano and nitro. These substituents preferably have a carbon number of 8 or less.

The group represented by -(M-Q) is preferably a group having 1 to 30 carbon atoms, more preferably a group having 5 to 20 carbon atoms. In particular, from the viewpoint of suppressing outgassing, a group having a carbon number of 6 or more is preferable.

A still further preferred embodiment of the group Y which is detached by the action of an acid is a structure represented by the following formula (III).

[Chemical 6]

In the formula, L ₃ , L ₄ and L ₅ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Among them, L ₃ , L ₄ and L ₅ are not all hydrogen atoms.

Furthermore, the cycloalkyl and aryl groups may contain heteroatoms.

Moreover, at least two of L ₃ , L ₄ and L ₅ may be bonded to each other to form a ring.

The alkyl group as L ₃ , L ₄ and L _{5 is} , for example, an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a hexyl group and an octyl group. .

The cycloalkyl group as L ₃ , L ₄ and L _{5 is} , for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

The aryl group as L ₃ , L ₄ and L ₅ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group and an anthracenyl group.

The aralkyl group as L ₃ , L ₄ and L _{5 is} , for example, an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include a benzyl group and a phenethyl group.

Examples of the cycloalkyl group and the aryl group containing a hetero atom of L ₃ , L ₄ and L ₅ include the same specific examples as the cycloalkyl group and the aryl group containing a hetero atom as Q.

L ₃ , L ₄ and L ₅ preferably each independently represent a hydrogen atom or an alkyl group, a cycloalkyl group or an aryl group, more preferably L ₃ to L ₅ are each an alkyl group or a cycloalkyl group, and further preferably L _{3 .} ~L ₅ is an alkyl group.

L ₃ , L ₄ and L ₅ in the formula (III) may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, and a thioether group. Mercapto, decyloxy, alkoxycarbonyl, cyano and nitro. These substituents preferably have a carbon number of 8 or less.

When at least two of L ₃ , L ₄ and L ₅ are bonded to each other to form a ring, the ring structure formed is preferably a monocyclic or polycyclic cycloalkyl group, more preferably a monocyclic cycloalkyl group. A 5-membered ring or a 6-membered ring of a monocyclic cycloalkyl group.

An example of the repeating unit represented by the formula (I) in which Y in the formula is a group represented by the formula (II) or the formula (III) is shown below.

[Chemistry 7]

[化8]

The content of the repeating unit represented by the above formula (I) in the polymer compound (A) of the present invention is preferably from 5 mol% to 60 mol% based on all the repeating units in the polymer compound (A). The range of the ear %, more preferably in the range of 10 mol% to 45 mol%, particularly preferably in the range of 15 mol% to 40 mol%.

The polymer compound (A) preferably further contains a repeating unit represented by the following formula (IV).

In the formula (IV), R ₄ represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom.

B ₂ represents a single bond or a divalent linking group.

Ar ₂ represents an (n+1)-valent aromatic ring group.

m represents an integer of 1 or more.

In the general formula (IV), examples of the substituent which the methyl group represented by R ₄ has may be the same as the specific examples and preferred ranges of the substituent which R _{1 of} the above formula (I) may have. base. As R _4, preferred is a hydrogen atom, a methyl group, more preferably a hydrogen atom.

The (m+1)-valent aromatic ring group represented by Ar ₂ in the formula (IV) is preferably an aromatic ring group having 6 to 18 carbon atoms. For example, the divalent aromatic ring group represented by Ar ₂ when m is 1 is preferably a phenyl group or a naphthyl group, and most preferably a phenyl group.

Further, the (m+1)-valent aromatic ring group represented by Ar ₂ may have a substituent other than the group represented by the -(OH) _m , and examples of the substituent include the above formula (I). The specific examples of the substituent which R ₁ may have and the substituents of the preferred range are the same.

m in the general formula (IV) is an integer of 1 or more, preferably an integer in the range of 1 to 5, and more preferably 1.

Further, in the general formula (IV), when m is 1 and Ar ₂ is a phenylene group, the bonding position of -OH with respect to the benzene ring of Ar ₂ relative to the bonding position of the benzene ring to the polymer main chain It can be a para position, a meta position or an adjacent position, preferably a para or meta position.

In the general formula (IV), the divalent linking group represented by B ₂ is, for example, the same as the specific examples and preferred ranges of the divalent linking group represented by M in the above formula (II).

The repeating unit represented by the above formula (IV) is preferably a repeating unit represented by the following formula (IV').

In the formula (IV'), R ₄ represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom. Ar ₂ represents an (n+1)-valent aromatic ring group. m represents an integer of 1 or more.

Formula (IV ') in R _4, Ar _2, and m are the same as in the general formula _{(IV) R 4, Ar 2} , and m meaning.

The repeating unit represented by the formula (IV) is a repeating unit having an alkali-soluble group and has a function of controlling the developability of the resist.

Preferred examples of the repeating unit of the formula (IV) are described below.

In the above, a preferred example of the repeating unit represented by the formula (IV) is a repeating unit in which Ar ₂ is an unsubstituted phenylene group, and the following are exemplified.

When the composition is a positive resist composition, the content of the repeating unit represented by the formula (IV) in the polymer compound (A) is preferably 3 in relation to all the repeating units in the polymer compound (A). Mohr%~90% by mole, more preferably 5% by mole to 90% by mole, and then preferably 7% by mole to 855% by mole.

The polymer compound (A) may further have a repeating unit other than the above-described repeating unit. As an example thereof, for example, a repeating unit which is stable with respect to the action of an acid as described below can be mentioned.

The repeating unit which is stable with respect to the action of the acid, more specifically, a styrene derivative having a non-acid-decomposable substituent as exemplified as the general formula (V), or as a general formula ( VI) is a repeating unit having a non-acid-decomposable aryl structure, a cycloalkyl structure, or a lactone structure, as exemplified in the side chain of the acrylonitrile-based structure. With this configuration, adjustment of contrast, improvement in etching resistance, and the like can be expected.

In the formula (V), Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. The alkyl group as Ra and Ra ₂ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group as Ra and Ra ₂ may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom or a chlorine atom. Examples of the alkyl group of Ra include a methyl group, a chloromethyl group, and a trifluoromethyl group.

Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

B in the formula (V) represents a mercapto group, an alkyl group, an alkoxy group, a mercaptooxy group or an alkoxycarbonyl group, preferably a mercaptooxy group or an alkoxycarbonyl group, more preferably a mercaptooxy group. Further, among the mercaptooxy groups (represented by the formula -O-CO-R _A ; R _A is an alkyl group), it is preferred that the carbon number of R _A is from 1 to 6, more preferably the carbon number of R _A For those of 1 to 3, it is particularly preferred that the carbon number of R _A is one (ie, ethoxylated).

p represents an integer of 0 to 5, preferably 0 to 2, more preferably 1 to 2, and even more preferably 1.

Each of the groups may have a substituent. Preferred examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group (methoxy group, and ethyl group). Oxyl, propoxy, butoxy, etc.). Further, examples of the cyclic structure include an alkyl group (preferably having 1 to 8 carbon atoms) as a substituent.

The polymer compound (A) may contain a repeating unit represented by the formula (V), or may not contain a repeating unit represented by the formula (V), and when it is contained, relative to all repeating units in the polymer compound (A) The content of the repeating unit represented by the formula (V) is preferably from 5 mol% to 30 mol%, more preferably from 5 mol% to 15 mol%.

Specific examples of the repeating unit represented by the general formula (V) are listed below, but are not limited to these specific examples.

In the formula (VI), R ₅ represents a non-acid-decomposable hydrocarbon group or a lactone group.

Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. The alkyl group as Ra and Ra ₂ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group as Ra and Ra ₂ may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom or a chlorine atom. Examples of the alkyl group of Ra include a methyl group, a chloromethyl group, and a trifluoromethyl group.

Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

R _{5 is} preferably a hydrocarbon group or a lactone group having a cyclic structure. Specific examples of the case having a cyclic structure include a monocyclic or polycyclic cycloalkyl group (preferably having a carbon number of 3 to 12, more preferably a carbon number of 3 to 7), and a monocyclic or polycyclic cycloalkenyl group. (preferably having a carbon number of 3 to 12), an aryl group (preferably having a carbon number of 6 to 20, more preferably a carbon number of 6 to 12), or an aralkyl group (preferably having a carbon number of 7 to 20, more preferably carbon) A number of 7 to 12), a monocyclic or polycyclic lactone group (preferably having a carbon number of 4 to 15, more preferably a carbon number of 4 to 10).

Each of the groups may further have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a halogen atom.

The polymer compound (A) may contain a repeating unit represented by the formula (VI), or may not contain a repeating unit represented by the formula (VI), and when it is contained, relative to all repeating units in the polymer compound (A) The content of the repeating unit represented by the formula (VI) is preferably from 1 mol% to 40 mol%, more preferably from 2 mol% to 20 mol%.

Specific examples of the repeating unit represented by the general formula (VI) are listed below, but the present invention is not limited to these specific examples. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Chemistry 16]

In the polymer compound (A) used in the present invention, it is preferable to further contain a group which generates an acid by irradiation with actinic rays or radiation in a side chain (hereinafter also referred to as a base). A repeating unit of "photoacid generating group"). In this case, the compound (B) which generates an acid by actinic ray or radiation, which is described later, is not an independent compound, but refers to a constituent component of the polymer compound (A) of the present invention. In other words, the polymer compound (A) further preferably contains a repeating unit having a group which generates an acid by irradiation with actinic rays or radiation in a side chain, and the polymer compound ( A) is the same compound as the compound (B) described below.

Examples of the repeating unit having a photoacid generating group include a repeating unit described in JP-A-H09-325497 (0028), or JP-A-2009-93137 (0038) to [0041]. Repeat unit. In this case, it is considered that the repeating unit having a photoacid generating group corresponds to the compound (B) which generates an acid by irradiation with actinic rays or radiation of the present invention.

The polymer compound (A) may contain a repeating unit having a photoacid generating group in a side chain, or may not contain a repeating unit having a photoacid generating group in a side chain, and when it is contained, relative to all of the polymer compound (A) The repeating unit preferably has a content of a repeating unit having a photoacid generating group in the side chain of from 1 mol% to 10 mol%, more preferably from 2 mol% to 8 mol%.

Examples of the repeating unit having a photoacid generating group in the side chain include a repeating unit represented by the following formula (5).

In the formula, R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. S represents a structural portion which is decomposed by irradiation of actinic rays or radiation and generates an acid in a side chain.

Specific examples of the repeating unit represented by the formula (5) are shown below, but the present invention is not limited to these specific examples.

[Chemistry 19]

[Chemistry 20]

[Chem. 21]

The polymer compound (A) of the present invention can be copolymerized with other polymerizable monomers capable of controlling film formability or solvent solubility.

Examples of the polymerizable monomers include hydrogenated hydroxystyrene, Maleic anhydride, acrylic acid derivatives (acrylic acid, acrylate, etc.), methacrylic acid derivatives (methacrylic acid, methacrylic acid ester, etc.), N-substituted maleimide, acrylonitrile, methyl Acrylonitrile or the like is not limited to these examples.

In addition, as a repeating unit of a preferable polymer compound, a unit having a cyclic structure in a main chain (a unit derived from a monomer having a fluorene structure, etc.) and a unit having a naphthol structure may be mentioned. a repeating unit having a -C(CF ₃ ) ₂ OH group or the like.

When the polymer compound (A) contains the repeating unit derived from the self-polymerizable monomer and the repeating unit, the content of the repeating unit is preferably 1 with respect to all the repeating units in the polymer compound (A). Molar%~30% by mole, more preferably 1% by mole to 10% by mole.

In the present invention, the polymer compound (A) may be used singly or in combination of two or more.

The mass average molecular weight of the polymer compound (A) used in the present invention is preferably 15,000 or less, more preferably the mass average molecular weight is in the range of 1,000 to 10,000, and particularly preferably in the range of 2,000 to 8,000.

When the molecular weight of the polymer compound is in the above range, sufficient analytical performance and LER performance can be obtained.

The degree of dispersion (Mw/Mn) of the polymer compound (A) is preferably in the range of 1.0 to 1.8, more preferably in the range of 1.0 to 1.5.

Here, the mass average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the polymer compound (A) are gel permeation chromatography (gel) based on polystyrene standards. Permeation chromatography. GPC) method (solvent: tetrahydrofuran (THF)).

The polymer compound (A) can be synthesized by a known radical polymerization method or an anionic polymerization method. For example, in the radical polymerization method, a vinyl monomer can be dissolved in a suitable organic solvent, and a peroxide (such as benzamidine peroxide) or a nitrile compound (azobisisobutylcarbonitrile or the like), or A redox compound (cumene hydroperoxide-ferrous salt) is used as a starter to carry out a reaction at room temperature or under heating to obtain a polymer. Further, in the anionic polymerization method, a vinyl monomer can be dissolved in a suitable organic solvent, and a metal compound (such as butyllithium) can be used as a starting agent, and usually a reaction is carried out under cooling to obtain a polymer.

Further, it is also possible to synthesize a polymer obtained by polymerizing a polymer using an unsaturated monomer corresponding to a precursor of each repeating unit, and then converting the polymer into a desired repeating unit by modifying the low molecular compound. In either case, living polymerization such as living anionic polymerization is used, whereby the molecular weight distribution of the obtained polymer compound becomes uniform, which is preferable.

Specific examples of the polymer compound described above are shown below, but the present invention is not limited to these specific examples.

[Chem. 24]

[化25]

In the specific example, tBu represents a third butyl group.

The content of the group which can be decomposed by the acid can be determined by the amount of the group which can be decomposed by the acid in the polymer compound (A) (B) and the amount of the alkali-soluble group which is not protected by the group which is desorbed by the acid (S) ), and is calculated by the formula B / (B + S). The content rate is better It is 0.01 to 0.7, more preferably 0.05 to 0.50, and further preferably 0.05 to 0.40.

The content of the polymer compound (A) in the composition is preferably 50% by mass to 95% by mass, and more preferably 55% by mass based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition. 92% by mass, and more preferably 60% by mass to 85% by mass.

[2] Compounds which generate acid by irradiation with actinic rays or radiation

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a compound which generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "acid generator (B)" or "compound (B). Further, it is preferable to contain a compound which generates an acid other than a carboxylic acid by irradiation with actinic rays or radiation. As the acid generator, a photoinitiator-based photoinitiator, a photoradical polymerization photoinitiator, a dye-based photodecolorizer, a photochromic agent, or a micro-resist can be suitably used. A known compound which produces an acid by irradiation with actinic rays or radiation and a mixture thereof.

The compound which decomposes by the irradiation of actinic ray or radiation to generate an acid as the acid generator (B) is represented by the following general formula (ZI), general formula (ZII), and general formula (ZIII). The compound is a preferred compound.

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

Z ^- represents a non-nucleophilic anion, preferably a sulfonate anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl)methide anion, BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- and the like, preferably an organic anion containing a carbon atom. The organic anion represented by the following formula AN1 to the following formula AN3 is exemplified as a preferred organic anion.

In the formula AN1 to the formula AN3, Rc ₁ to Rc ₃ each independently represent an organic group.

Examples of the organic group in Rc ₁ to Rc ₃ include those having 1 to 30 carbon atoms, preferably a substituted alkyl group, a substituted aryl group, or a plurality of such a single bond, -O. -, -CO ₂ -, -S-, -SO ₃ -, -SO ₂ N(Rd ₁ )- and the like are bonded to each other. Further, it may form a ring structure with other bonded alkyl groups and aryl groups.

Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with other bonded alkyl groups or aryl groups.

The organic group of Rc ₁ to Rc ₃ may be an alkyl group substituted with a fluorine atom or a fluoroalkyl group at one position, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation increases, and the sensitivity is improved. When Rc ₁ to Rc ₃ have 5 or more carbon atoms, it is preferred that at least one carbon atom is substituted with a hydrogen atom, and more preferably, the number of hydrogen atoms is more than that of the fluorine atom. By having no perfluoroalkyl group having a carbon number of 5 or more, the ecological toxicity is alleviated.

The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a carbon number of usually 1 to 30, preferably 1 to 20.

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring.

Examples of the group formed by the two bonds in R ₂₀₁ to R ₂₀₃ include an alkyl group (for example, a butyl group and a pentyl group).

Specific examples of the organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compound (ZI-1), the compound (ZI-2) and the compound (ZI-3) to be described later.

Further, it may be a compound having a plurality of structures represented by the general formula (ZI). For example, compounds having the structure may also be: R compounds of formula (ZI) is represented by at least one of R ₂₀₁ ~ R another compound of the general formula (ZI) ₂₀₃ is represented by at least a ₂₀₁ ~ R ₂₀₃ Bonded structure.

Further preferred examples of the (ZI) component include the compound (ZI-1), the compound (ZI-2), and the compound (ZI-3) described below.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ of the above formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as a cation.

In the arylsulfonium compound, R ₂₀₁ to R ₂₀₃ may each be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group and the remainder may be an alkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound and a diaryl group. Alkyl hydrazine compound, aryl dialkyl hydrazine compound.

The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, a heteroaryl group such as an anthracene residue or a pyrrole residue, and further preferably a phenyl group or a hydrazine residue. When the arylsulfonium compound has two or more aryl groups, two or more aryl groups may be the same or different.

The alkyl group or cycloalkyl group which the aryl hydrazine compound has as needed is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a methyl group and an ethyl group. , propyl, n-butyl, t-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclohexyl and the like.

The aryl group or the alkyl group as R ₂₀₁ to R ₂₀₃ may have an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), an aryl group (for example, a carbon number of 6 to 14), and an alkoxy group. A group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group, or a phenylthio group is used as a substituent. Preferred substituents are a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, preferably It is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted for any of the three R ₂₀₁ to R ₂₀₃ , or all of the three may be substituted. Further, when R ₂₀₁ to R ₂₀₃ are an aryl group, the substituent is preferably substituted for the para position of the aryl group.

Next, the compound (ZI-2) will be described.

The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represent an organic group which does not contain an aromatic ring. The aromatic ring herein also includes an aromatic ring containing a hetero atom.

The organic group which does not contain an aromatic ring as R ₂₀₁ to R ₂₀₃ is usually a carbon number of 1 to 30, preferably a carbon number of 1 to 20.

R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, a vinyl group, and more preferably a linear 2-oxoalkyl group. And a branched 2-oxoalkyl group, a cyclic 2-oxoalkyl group, an alkoxycarbonylmethyl group, preferably a linear 2-oxoalkyl group or a branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be either a straight chain or a branched group, and preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, or butyl group). Base, pentyl). Examples of the cycloalkyl group of R ₂₀₁ to R ₂₀₃ include a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, and norbornyl group).

The 2-oxoalkyl group as R ₂₀₁ to R ₂₀₃ may be any of a straight chain, a branched group, and a cyclic group, and is preferably exemplified by the alkyl group or the cycloalkyl group having >C=O. base.

The alkoxy group in the alkoxycarbonylmethyl group of R ₂₀₁ to R ₂₀₃ is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentane group). Oxy).

R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group.

Two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond, or a carbonyl group in the ring. Examples of the group formed by the two bonds in R ₂₀₁ to R ₂₀₃ include an alkyl group (for example, a butyl group and a pentyl group).

Next, the compound (ZI-3) will be described.

The compound (ZI-3) is a compound represented by the following formula (ZI-3), and is a compound having a benzamidine methyl phosphonium salt structure.

R ₁ c to R ₅ c each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.

R ₆ c and R ₇ c each independently represent a hydrogen atom or an alkyl group.

Rx and Ry each independently represent an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group.

Any two or more of R ₁ c to R ₇ c may be bonded to form a ring structure. Moreover, Rx and Ry may be bonded to form a ring structure. The ring structures may include an oxygen atom, a sulfur atom, an ester bond, and a guanamine bond.

X ^- is the same as Z ^- in the formula (ZI).

Specific examples of the compound (ZI-3) include the compounds exemplified in paragraph 0047 to paragraph 0046 of JP-A-2004-233661, and paragraphs 0040 to 0046 of JP-A-2003-35948. .

Next, the general formula (ZII) and the general formula (ZIII) will be described.

In the general formula (ZII) and the general formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group which may have a substituent, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent.

Specific examples and preferred examples of the aryl group of R ₂₀₄ to R ₂₀₇ are the same as those described for the aryl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI-1).

Specific examples and preferred examples of the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ and the linear or branched alkyl group and cycloalkyl group as R ₂₀₁ to R ₂₀₃ in the compound (ZI-2) The explanation is the same.

Z ^- in general formula (ZI) in the Z ^- the same meaning.

Preferred compounds in the compound which generates an acid by irradiation with actinic rays or radiation as the acid generator (B) may further include the following general formula (ZIV), general formula (ZV), and general formula (ZVI). The compound represented.

In the general formula (ZIV) to the general formula (ZVI), Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.

R ₂₀₈ independently represents, by the formula (ZV) and the formula (ZVI), a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group. . In terms of increasing the strength of the acid produced, R _{208 is} preferably substituted with a fluorine atom.

R ₂₀₉ and R ₂₁₀ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or an electron-withdrawing group. As R ₂₀₉ , a substituted or unsubstituted aryl group is preferred. R _{210 is} preferably an electron withdrawing group, more preferably a cyano group or a fluoroalkyl group.

A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted extended alkenyl group, or a substituted or unsubstituted extended aryl group.

Further, in the present invention, a compound having a plurality of structures represented by the formula (ZVI) is also preferred. Any one of R compounds of formula (ZVI) represented by any one of R ₂₀₉ or R ₂₁₀ of another compound of a general formula (ZVI) represented by R ₂₀₉ or _210: Compound e.g., having the following structure may also be Bonded structure.

The compound represented by the formula (ZI) to the formula (ZIII) is more preferably a compound which is decomposed by irradiation with actinic rays or radiation to generate an acid other than a carboxylic acid, and is preferably a compound represented by the formula (ZI) to (ZIII). Further, the compound represented by the formula (ZI) is preferably a compound represented by (ZI-1) to (ZI-3).

Specific examples of the acid generator (B) are shown below, but are not limited to these specific examples.

[化32]

[化33]

[化34]

[化35]

The acid generator (B) may be used alone or in combination of two or more. When two or more types are used in combination, it is preferred to combine a compound having two or more total atoms other than a hydrogen atom and producing two different organic acids.

The content of the acid generator (B) in the composition is preferably from 5% by mass to 50% by mass, more preferably 8% by mass based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition. 40% by mass, and more preferably 10% by mass to 40% by mass.

[3] Basic compounds

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound. The basic compound is preferably a compound which is more basic than phenol. The basic compound is preferably an organic basic compound, and further preferably a nitrogen-containing basic compound. Further, in one aspect, a phosphonium salt which relatively becomes a weak acid with respect to the acid generator can also be used as the basic compound.

The nitrogen-containing basic compound which can be used is not particularly limited, and for example, the compounds classified as the following (1) to (7) can be used, and among them, the (4) ammonium salt described later is preferable.

(1) a compound represented by the general formula (BS-1)

In the general formula (BS-1), R independently represents a hydrogen atom or an organic group. Among them, at least one of the three R is an organic group. The organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group or an aralkyl group.

The description of the compound represented by the formula (BS-1) (the description of each group, the specific example of the compound represented by the formula (BS-1), etc.) can be referred to the paragraph of JP-A-2013-015572 The description of paragraph 0471 to paragraph 0481 is incorporated into the specification of the present application.

(2) Compounds having a nitrogen-containing heterocyclic structure

The nitrogen-containing heterocyclic ring may have aromaticity or may not be aromatic. and, It may also have a plurality of nitrogen atoms. Further, it may contain a hetero atom other than nitrogen. Specific examples thereof include a compound having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), a compound having a piperidine structure [N-hydroxyethylpiperidine, and a double (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, etc., a compound having a pyridine structure (4-dimethylaminopyridine, etc.), and having an antipyre An antipyrine structure of compounds (antipyrine and hydroxyantipyrine, etc.).

Examples of preferred compounds having a nitrogen-containing heterocyclic ring structure include hydrazine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, anthracene, imidazole, pyrazole, pyrazine, pyrimidine, anthracene, Imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. These may further have a substituent.

Preferred examples of the substituent include an amine group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, a decyl group, a decyloxy group, an aryl group, and the like. Aryloxy, nitro, hydroxy and cyano groups.

As a particularly preferable basic compound, for example, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4, 5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino group- 6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine, N-(2- Aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1-(2-amino group Ethyl pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolyl Pyrazole, pyrazine, 2-(aminomethyl)-5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyridyl Oxazoline, N-aminomorpholine and N-(2-aminoethyl)morpholine.

Further, a compound having two or more ring structures can also be suitably used. Specific examples thereof include 1,5-diazabicyclo[4.3.0]non-5-ene and 1,8-diazabicyclo[5.4.0]undec-7-ene.

(3) Amine compounds having a phenoxy group

The amine compound having a phenoxy group means a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group may have, for example, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, a decyloxy group, an aryloxy group, or the like. Substituent.

More preferably, the compound has at least one oxygen alkyl chain between the phenoxy group and the nitrogen atom. The number of oxygen-extended alkyl chains in one molecule is preferably from 3 to 9, and preferably from four to six. Among the oxygen-extended alkyl chains, particularly preferred is -CH ₂ CH ₂ O-.

Specific examples include 2-[2-{2-(2,2-dimethoxy-phenoxyethoxy)ethyl}-bis-(2-methoxyethyl)]-amine. And the compound (C1-1) to the compound (C3-3) exemplified in paragraph [0066] of the specification of US2007/0224539A1.

The amine compound having a phenoxy group can be obtained, for example, by heating a primary or secondary amine having a phenoxy group and a halogenated alkyl ether to react with sodium hydroxide, potassium hydroxide and tetraoxane. After the aqueous solution of a strong base such as ammonium is used, the mixture is extracted with an organic solvent such as ethyl acetate or chloroform. Moreover, an amine compound having a phenoxy group can also be obtained by having a phenoxy group for the primary or secondary amine and the terminal. The halogenated alkyl ether is heated and reacted, and after adding an aqueous solution of a strong alkali such as sodium hydroxide, potassium hydroxide or tetraalkylammonium, it is extracted with an organic solvent such as ethyl acetate or chloroform.

(4) ammonium salt

As the basic compound, an ammonium salt can be suitably used, and a quaternary ammonium salt is preferred.

The cation of the ammonium salt is preferably a tetraalkylammonium cation substituted with an alkyl group having 1 to 18 carbon atoms, more preferably a tetramethylammonium cation, a tetraethylammonium cation or a tetrakis (n-propyl)ammonium cation. Tetrakis(isopropyl)ammonium cation, tetra(n-butyl)ammonium cation, tetra(n-heptyl)ammonium cation, tetra(n-octyl)ammonium cation, dimethylhexadecyl ammonium cation, benzyltrimethyl A quaternary ammonium cation or the like is preferably a tetra(n-butyl)ammonium cation.

Examples of the anion of the ammonium salt include a hydroxide, a carboxylate, a halide, a sulfonate, a borate, and a phosphate. Among these, a hydroxide or a carboxylate is particularly preferred.

As the halide, ethyl chloride, bromide and iodide are particularly preferred.

As the sulfonate, an organic sulfonate having a carbon number of 1 to 20 is particularly preferred. Examples of the organic sulfonate include an alkylsulfonate having 1 to 20 carbon atoms and an arylsulfonate.

The alkyl group contained in the alkyl sulfonate may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, a fluorenyl group, and an aryl group. Specific examples of the alkyl sulfonate include methanesulfonate, ethanesulfonate, butanesulfonate, hexanesulfonate, octanesulfonate, benzylsulfonate, and trifluoromethane. Sulfonate, pentafluoroethane sulfonate and nonafluorobutane sulfonate.

Examples of the aryl group contained in the arylsulfonate include a phenyl group and a naphthyl group. And 蒽基. The aryl groups may have a substituent. The substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms. Specifically, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a n-hexyl group, and a cyclohexyl group are preferable. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, a decyl group, and a decyloxy group.

The carboxylate may be an aliphatic carboxylic acid salt or an aromatic carboxylic acid salt, and examples thereof include an acetate, a lactate, a pyruvate, a trifluoroacetate, an adamantane carboxylate, and a hydroxyadamantanecarboxylic acid. Salt, benzoate, naphthoate, salicylate, phthalate, phenolate, etc., particularly preferably benzoate, naphthoate, phenolate, etc. The best is benzoate.

In this case, as the ammonium salt, tetra (n-butyl) ammonium benzoate or tetrakis (n-butyl) phenol ammonium or the like is preferable.

In the case of hydroxides, the ammonium salt is particularly preferably a tetraalkylammonium hydroxide having a carbon number of 1 to 8 (tetramethylammonium hydroxide and tetraethylammonium hydroxide, tetra(n-butyl)ammonium hydroxide. Etc. tetraalkylammonium hydroxide).

(5) A compound (PA) having a proton-receptive functional group and which is decomposed by irradiation with actinic rays or radiation and which produces a compound having reduced proton acceptability, disappearance or acidity change from proton acceptor.

The composition of the present invention may further contain a compound as a basic compound having a proton-receptive functional group and decomposed by irradiation with actinic rays or radiation to cause a decrease in proton acceptor, disappearance or by a proton acceptor. A compound which is a compound which changes in acidity (hereinafter also referred to as a compound (PA)).

As a compound (PA) having a proton-receptive functional group and decomposing by irradiation with actinic rays or radiation and causing a decrease in proton acceptor property, disappearance, or acidity change from proton acceptor, refer to Japan. JP-A-2012-32762, paragraph 0379 to paragraph 0425 (corresponding to the description of [0386] to [0435] of the corresponding US Patent Application Publication No. 2012/0003590), the contents of which are hereby incorporated herein. in.

In the composition of the present invention, the compounding ratio of the compound (PA) in the entire composition is preferably from 0.1% by mass to 10% by mass, and more preferably from 1% by mass to 8% by mass based on the total solid content.

(6) bismuth compound

The composition of the present invention may further contain a ruthenium compound.

As the ruthenium compound, the contents of the [0382] to [0385] of the specification of the corresponding US Patent Application Publication No. 2012/0003590, the contents of which are incorporated herein by reference. Incorporated into the specification of the present application.

(7) a low molecular compound having a nitrogen atom and having a group which is desorbed by the action of an acid

The composition of the present invention may contain a low molecular compound having a nitrogen atom and having a group which is desorbed by the action of an acid (hereinafter also referred to as "low molecular compound (D)" or "compound (D)"). The low molecular compound (D) is preferably basic after being detached from the group which is detached by the action of an acid.

As a low molecular compound (D), refer to the Japanese Patent Special The contents of paragraphs 0324 to 0337 of the Japanese Patent Publication No. 2012-133331 are incorporated herein by reference.

In the present invention, the low molecular compound (D) may be used alone or in combination of two or more.

The composition of the present invention may contain the low molecular compound (D) or may not contain the low molecular compound (D), and when contained, the compound (D) based on the total solid content of the composition combined with the basic compound The content is usually 0.001% by mass to 20% by mass, preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass.

Further, when the composition of the present invention contains an acid generator, the ratio of the acid generator to the compound (D) used in the composition is preferably an acid generator / [compound (D) + the following basic compound] (Mo Ear ratio) = 2.5~300. In other words, in terms of the sensitivity and the resolution, it is preferable that the molar amount is 2.5 or more, and the aspect of reducing the resolution due to the coarseness of the resist pattern over time after the post-exposure heat treatment is suppressed. The ear is preferably less than 300. The acid generator / [compound (D) + the basic compound] (mole ratio) is more preferably 5.0 to 200, and further preferably 7.0 to 150.

In addition, as a composition of the present invention, a compound synthesized in the examples of JP-A-2002-363146, and a paragraph 0108 in JP-A-2007-298569 can be cited. Compounds, etc.

As the basic compound, a photosensitive basic compound can also be used. As the photosensitive basic compound, for example, Japanese Patent Laid-Open No. 2003-524799 can be used. The publications and the compounds described in "J. Photopolym. Sci & Tech." Vol. 8, P. 543-553 (1995) and the like.

The onium salt which is relatively weakly acidic to the acid generator is preferably a compound represented by the following formula (d1-1) to formula (d1-3).

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (wherein a fluorine atom is not substituted on a carbon atom adjacent to S), R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkyl or aryl group, Rf is a hydrocarbon group containing a fluorine atom, and M ^{+ is} independently a phosphonium cation or a phosphonium cation.

Preferable examples of the phosphonium cation or the phosphonium cation represented by M ⁺ include a phosphonium cation exemplified in the general formula (ZI) and a phosphonium cation exemplified in the general formula (ZII).

A preferred example of the anion portion of the compound represented by the formula (d1-1) is a structure exemplified in paragraph [0198] of JP-A-2012-242799.

A preferred example of the anion portion of the compound represented by the formula (d1-2) is a structure exemplified in paragraph [0201] of JP-A-2012-242799.

Preferred examples of the anion portion of the compound represented by the formula (d1-3) include those exemplified in paragraph [0209] and paragraph [0210] of JP-A-2012-242799.

The onium salt which is relatively weakly acidic with respect to the acid generator may be (C) a compound having a cationic site and an anion site in the same molecule, and the cationic site and the anion site are linked by a covalent bond (hereinafter also referred to as It is "compound (CA)").

The compound (CA) is preferably a compound represented by any one of the following formulae (C-1) to (C-3).

In the general formulae (C-1) to (C-3), R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms.

L ₁ represents a divalent linking group or a single bond linking a cationic moiety to an anionic moiety.

-X ^- represents an anion moiety selected from the group consisting of -COO ^- , -SO ₃ ^- , -SO ₂ ^- , -N ^- -R ₄ . R ₄ represents a group having a carbonyl group at a point of bonding to an adjacent N atom: -C(=O)-, sulfonyl group: -S(=O) ₂ -, sulfinyl group: -S(=O)- The substituent of the valence.

R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. Further, in (C-3), two of R ₁ to R ₃ may be bonded to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, and an alkylamine. A carbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group or the like. Preferred are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as a divalent linking group may, for example, be a linear or branched alkyl group, a cycloalkyl group, an extended aryl group, a carbonyl group, an ether bond, an ester bond, a guanamine bond or a urethane bond, A urea bond, a group in which two or more of these are combined, and the like. L _{1 is more} preferably an alkyl group, an aryl group, an ether bond, an ester bond, or a combination of two or more of these.

Preferred examples of the compound represented by the formula (C-1) include paragraphs [0037] to [0039] of JP-A-2013-6827, and JP-A-2013-8020. The compound exemplified in paragraph [0027] to paragraph [0029].

Preferable examples of the compound represented by the formula (C-2) include the compounds exemplified in paragraphs [0012] to [0013] of JP-A-2012-189977.

Preferable examples of the compound represented by the formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP-A-2012-252124.

The content of the cerium salt which becomes relatively weak acid with respect to the acid generator is preferably 0.5% by mass to 10.0% by mass, and more preferably 0.5, based on the solid content of the composition. The mass % to 8.0% by mass, and more preferably 1.0% by mass to 8.0% by mass.

The molecular weight of the basic compound is usually from 100 to 1,500, preferably from 150 to 1300, more preferably from 200 to 1,000.

These basic compounds may be used alone or in combination of two or more.

When the composition of the present invention contains a basic compound, the content thereof is preferably from 0.01% by mass to 10.0% by mass based on the total solid content of the composition, more preferably from 0.1% by mass to 8.0% by mass, particularly preferably 0.2% by mass. Mass%~5.0% by mass.

The molar ratio of the basic compound to the acid generator is preferably from 0.01 to 10, more preferably from 0.05 to 5, and even more preferably from 0.1 to 3. If the molar ratio is excessively increased, the sensitivity and/or resolution may be lowered. If the molar ratio is excessively reduced, a reduction in pattern may occur between exposure and heating (post-baking). More preferably 0.05 to 5, and thus preferably 0.1 to 3. In addition, the acid generator in the molar ratio is based on the total amount of the repeating unit represented by the formula (5) of the resin and the acid generator which may be further contained in the resin.

[4] surfactant

The composition of the present invention may further contain a surfactant. When it is contained, as a surfactant, a fluorine-based and/or a lanthanoid surfactant is preferable.

Examples of the surfactants mentioned above include Megafac F176, Megafac R08, PF656, PF6320, and Troy Chemical manufactured by Dainippon Ink Chemical Industry Co., Ltd. Troy Sol S-366, manufactured by Troy Chemical Co., Ltd. Suvor 3F (share) made by Fluorad FC430, Shin-Etsu Chemical Industry Co., Ltd. produced polyoxyalkylene polymer KP-341 and so on.

Further, other surfactants other than fluorine-based and/or lanthanoid surfactants may be used. More specifically, polyoxyethylene ethyl ethers, polyoxyethylene ethyl aryl ethers, and the like can be mentioned.

In addition to the above, a known surfactant can be suitably used. As the surfactant which can be used, for example, the surfactant described in [0273] and later on the specification of the US Patent Application Publication No. 2008/0248425 A1 can be mentioned.

The surfactants may be used singly or in combination of two or more.

The amount of the surfactant added is preferably from 0% by mass to 2% by mass, and more preferably 0.0001% by mass, based on the total solid content of the photosensitive ray-sensitive or radiation-sensitive resin composition (except for the total amount of the solvent). ~2% by mass, particularly preferably 0.0005% by mass to 0.5% by mass.

[5] Hydrophobic resin

The composition of the present invention may also contain a hydrophobic resin.

The hydrophobic resin is preferably designed to be present on the surface of the sensitizing ray-sensitive or radiation-sensitive film, but unlike the surfactant, it is not necessarily required to have a hydrophilic group in the molecule, and it does not contribute to the polar substance/non- The polar substances are uniformly mixed.

Examples of the effect of adding the hydrophobic resin include controlling the sensitizing ray property or the static/dynamic contact angle with respect to water on the surface of the radiation sensitive film, suppressing outgassing, and the like.

In view of the fact that the hydrophobic resin is present in the surface layer of the film, the hydrophobic resin preferably has at least one of a "fluorine atom", a "deuterium atom", and a "CH ₃ partial structure contained in a side chain portion of the resin". There are two or more types of good.

When the hydrophobic resin contains a fluorine atom and/or a ruthenium atom, the fluorine atom and/or the ruthenium atom in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin contains a fluorine atom, it is preferably a resin having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group, or a fluorine atom-containing aryl group as a partial structure containing a fluorine atom.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a fluorine atom. Substituent.

The cycloalkyl group containing a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

The aryl group containing a fluorine atom may be one in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

Examples of the repeating unit containing a fluorine atom or a ruthenium atom are exemplified in paragraph 0519 of US2012/0251948A1.

Further, as described above, the hydrophobic resin preferably further contains a CH ₃ moiety structure in the side chain portion.

Here, the side chain portion of the hydrophobic resin contained in the partial structure CH ₃ (hereinafter also referred to as "partial structure a side chain CH ₃ ') contains a partial structure CH ₃ ethyl, propyl and the like contained.

On the other hand, a methyl group directly bonded to a main chain of a hydrophobic resin (for example, an α-methyl group having a repeating unit of a methacrylic acid structure) has a contribution to the surface of the hydrophobic resin due to the influence of the main chain. It is small and therefore is set in the CH ₃ partial structure which is not included in the present invention.

More specifically, the hydrophobic resin includes, for example, a repeating unit represented by the following formula (M): a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, and R ₁₁ to R _{When 14} is CH ₃ "self", the CH _{3 is} not included in the CH ₃ moiety structure contained in the side chain moiety in the present invention.

On the other hand, the CH ₃ partial structure existing from the CC main chain via some atoms is set to correspond to the CH ₃ partial structure in the present invention. For example, when R ₁₁ is ethyl (CH ₂ CH ₃ ), it is assumed to have "one" CH ₃ partial structure in the present invention.

In the above formula (M), R ₁₁ to R ₁₄ each independently represent a side chain moiety.

Examples of R ₁₁ to R ₁₄ which are side chain moieties include a hydrogen atom, a monovalent organic group and the like.

Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, and an alkylaminocarbonyl group. And a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, or the like, which may further have a substituent.

The hydrophobic resin is preferably a resin having a repeating unit having a CH ₃ partial structure in a side chain portion, more preferably a repeating unit represented by the following formula (VII), and a formula represented by the following formula (VIII) At least one repeating unit (x) in the repeating unit is taken as such a repeating unit.

Hereinafter, the repeating unit represented by the formula (VII) will be described in detail.

In the above formula (VII), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents an organic group having one or more CH ₃ partial structures and being stable to an acid. More specifically, the organic group which is stable to the acid is preferably an organic group which does not have the "acid-decomposable group" described in the resin (A).

The alkyl group of X _b1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a methyl group is preferable.

X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group having at least one CH ₃ partial structure, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group may further have an alkyl group as a substituent.

R _{2 is} preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.

The organic group having one or more CH ₃ partial structures of R ₂ and being stable to an acid preferably has two or more and ten or less CH ₃ partial structures, more preferably two or more and eight or less. The structure of the CH ₃ part.

Preferred specific examples of the repeating unit represented by the formula (VII) are listed below. Furthermore, the present invention is not limited to this.

[化41]

The repeating unit represented by the formula (VII) is preferably a (non-acid-decomposable) repeating unit which is stable to an acid, and specifically, preferably has no group which decomposes due to the action of an acid and generates a polar group. Repeat unit.

Hereinafter, the repeating unit represented by the formula (VIII) will be described in detail.

[化42]

In the above formula (VIII), X _b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₃ represents an organic group having one or more CH ₃ partial structures and being stable to an acid, and n represents 1~ An integer of 5.

The alkyl group of X _b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group.

X _{b2 is} preferably a hydrogen atom.

R ₃ is an organic group which is stable to an acid, and therefore, more specifically, it is preferably an organic group which does not have the "acid-decomposable group" described in the above resin (A).

Examples of R ₃ include an alkyl group having one or more CH ₃ partial structures.

The organic group having one or more CH ₃ partial structures of R ₃ and being stable to an acid preferably has one or more and ten or less CH ₃ partial structures, and more preferably one or more and eight or less. The CH ₃ partial structure preferably further has one or more and four or less CH ₃ partial structures.

n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and more preferably 1 or 2.

Preferred specific examples of the repeating unit represented by the formula (VIII) are listed below. Furthermore, the present invention is not limited to this.

[化43]

The repeating unit represented by the formula (VIII) is preferably a (non-acid-decomposable) repeating unit which is stable to an acid, and specifically, preferably has no group which decomposes due to the action of an acid and generates a polar group. Repeat unit.

When the hydrophobic resin contains a CH ₃ partial structure in a side chain portion, and further, particularly when there is no fluorine atom or a ruthenium atom, the repeating unit represented by the general formula (VII), and The content of at least one repeating unit (x) in the repeating unit represented by the formula (VIII) is preferably 90 mol% or more, more preferably 95 mol% or more. The content is usually 100 mol% or less with respect to all the repeating units of the hydrophobic resin.

The hydrophobic resin contains 90 mol% or more of the repeating unit represented by the formula (VII) and at least one repeating unit represented by the formula (VIII), with respect to all the repeating units of the hydrophobic resin. (x), the surface free energy of the hydrophobic resin is increased. As a result, the hydrophobic resin tends to be biased toward the surface of the photosensitive ray-sensitive or radiation-sensitive film.

Further, the hydrophobic resin may have at least one selected from the group consisting of (i) containing a fluorine atom and/or a ruthenium atom, and (ii) a side chain moiety having a CH ₃ moiety structure. )~ The base in the group of (z) below.

(x) acid group, (y) a group containing a lactone structure, an acid anhydride group, or a quinone imine group, (z) a group decomposed by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamino group, a sulfonyl fluorenylene group, or an alkyl sulfonyl group. Methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indolyl, bis(alkylsulfonyl) a methylene group, a bis(alkylsulfonyl) fluorenylene group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group, and the like.

Preferred examples of the acid group include a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonimide group, and a bis(alkylcarbonyl)methylene group.

Examples of the repeating unit having an acid group (x) include a repeating unit in which an acid group is directly bonded to a main chain of the resin, such as a repeating unit formed of acrylic acid or methacrylic acid, or a resin via a linking group. A repeating unit having an acid group bonded to the main chain or the like may be used, and a polymerization initiator or a chain transfer agent having an acid group may be used for introduction to the end of the polymer chain during polymerization, and any of them is preferred. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a germanium atom.

The content of the repeating unit having an acid group (x) is preferably from 1 mol% to 50 mol%, more preferably from 3 mol% to 35 mol%, and further preferably relative to all repeating units in the hydrophobic resin. It is 5 mol%~20 mol%.

Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

[化44]

The group containing a lactone structure, an acid anhydride group, or a quinone imine group (y) is particularly preferably a group having a lactone structure.

The repeating unit containing these groups is, for example, a repeating unit in which the group is directly bonded to the main chain of the resin, such as a repeating unit formed of acrylate or methacrylate. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced to the end of the resin by using a polymerization initiator or a chain transfer agent having the group at the time of polymerization.

The repeating unit having a group having a lactone structure may, for example, be the same as the repeating unit having a lactone structure described in the previous resin (A).

The content of the repeating unit having a lactone-containing group, an acid anhydride group or a quinone imine group is preferably from 1 mol% to 100 mol%, more preferably 3, based on all repeating units in the hydrophobic resin. Mohr%~98% by mole, and more preferably 5% by mole to 95% by mole.

The repeating unit having a group (z) which is decomposed by the action of an acid in the hydrophobic resin is the same as the repeating unit having an acid-decomposable group exemplified in the resin (A). The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a germanium atom. The content of the repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin is preferably from 1 mol% to 80 mol%, more preferably 10, with respect to all the repeating units in the hydrophobic resin. Molar% to 80% by mole, and more preferably 20% by mole to 60% by mole.

When the hydrophobic resin has a fluorine atom, the content of the fluorine atom is preferably from 5% by mass to 80% by mass based on the mass average molecular weight of the hydrophobic resin, more preferably 10% by mass to 80% by mass. Further, in all the repeating units contained in the hydrophobic resin, the repeating unit containing a fluorine atom is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%.

When the hydrophobic resin has a ruthenium atom, the content of the ruthenium atom is preferably from 2% by mass to 50% by mass, and more preferably from 2% by mass to 30% by mass based on the mass average molecular weight of the hydrophobic resin. Further, among all the repeating units contained in the hydrophobic resin, the repeating unit containing a halogen atom is preferably from 10 mol% to 100 mol%, more preferably from 20 mol% to 100 mol%.

On the other hand, in particular, when the hydrophobic resin contains a CH ₃ partial structure in a side chain portion, the hydrophobic resin does not substantially contain a fluorine atom and a ruthenium atom, and in this case, specifically, relative to hydrophobicity The content of the repeating unit containing a fluorine atom or a ruthenium atom in all the repeating units in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, further preferably 1 mol% or less, and desirably 0 mol. The ear %, that is, does not contain a fluorine atom and a germanium atom. Further, the hydrophobic resin preferably contains substantially only a repeating unit which contains only an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom. More specifically, in all the repeating units of the hydrophobic resin, the repeating unit containing only an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is preferably 95 mol% or more, more preferably It is 97% by mole or more, and more preferably 99% by mole or more, and desirably 100% by mole.

The standard polystyrene-equivalent mass average molecular weight of the hydrophobic resin is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, and still more preferably from 2,000 to 15,000.

Further, one type of the hydrophobic resin may be used, or a plurality of them may be used in combination.

The content of the hydrophobic resin in the composition is preferably from 0.01% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, even more preferably 0.1% by mass based on the total solid content of the composition of the present invention. %~7 mass%.

The amount of impurities such as metal of the hydrophobic resin is naturally small, and the residual monomer or oligomer component is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass, and still more preferably 0.05% by mass to 1% by mass. quality%. Thereby, a composition which does not have a foreign matter in the liquid or does not have a change in sensitivity or the like with time can be obtained. Further, the molecular weight distribution (Mw/Mn, also referred to as dispersion degree) is preferably in the range of 1 to 5 in terms of resolution, resist shape, side wall of the resist pattern, roughness, and the like, and more preferably The range of 1~3 is better than the range of 1~2.

The hydrophobic resin can also be synthesized by various commercially available products or by a conventional method such as radical polymerization. For example, as a general synthesis method, a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and heated to carry out polymerization is used, and the monomer species and the initiator are used in 1 hour to 10 hours. The dropwise addition of the solution to the heating solvent, etc., is preferably a dropwise addition polymerization method.

The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.), and the purification method after the reaction are the same as those described in the resin (A), but in the synthesis of the hydrophobic resin, the reaction concentration is preferred. It is 30% by mass to 50% by mass.

[6] A compound having a monovalent iodine atom

The composition of the present invention may also contain a compound (AD) having a monovalent iodine atom. The sensitivity is improved by the composition containing the compound (AD). As a compound (AD), for example, (AD1) a resin having a monovalent iodine atom (hereinafter also referred to as "resin (AD1)"), and (AD2) a low molecular compound having a monovalent iodine atom (hereinafter) Also known as "low molecular compound (AD2)"). The resin (A) may also serve as a resin (AD1).

<(AD1) Resin having a monovalent iodine atom>

The resin (AD1) having a monovalent iodine atom contained in the composition is preferably a resin containing a repeating unit (s) having a monovalent iodine atom, which will be described later.

The content of the repeating unit (s) in the resin (AD1) (which is a total when it is contained) is preferably from 5 mol% to 100 mol%, relative to all the repeating units in the resin (AD1). It is 10% by mole to 100% by mole, and then 20% by mole to 100% by mole.

Further, the resin (AD1) may contain the same repeating unit as that described for the repeating unit which may be contained in the resin (A), and the content of the repeating units in the resin (AD1) is also the same as that of the resin (A).

In the composition, the resin (AD1) may be used alone or in combination of two or more. The content of the resin (AD1) is preferably from 0.1% by mass to 50% by mass, more preferably from 0.1% by mass to 30% by mass, even more preferably from 1% by mass to 10% by mass based on the total solid content of the composition. .

<(AD2) Low Molecular Compound with Monovalent Iodine Atom>

The low molecular compound (AD2) having a monovalent iodine atom may, for example, be a compound having a monovalent iodine atom having a molecular weight of less than 3,000, preferably having a small molecular weight. The compound of 2000 is more preferably a compound having a molecular weight of less than 1,500, and further preferably a compound having a molecular weight of less than 1,000. The low molecular compound (AD2) having a monovalent iodine atom is, for example, a compound represented by the following formula (2').

Ar ₂ -(RI) _n (2')

In the formula (2'), Ar ₂ represents an n-valent aromatic ring group.

RI represents an iodine atom or an organic group containing at least one iodine atom.

n represents an integer of 1 or more.

The aromatic ring group represented by Ar ₂ is an n-valent aromatic ring group.

Examples of the monovalent aromatic ring group when n is 1 may, for example, be a phenyl group, a tolyl group, a naphthyl group, an anthracenyl group, a biphenyl group or a stilbene group. Or a heterocyclic ring containing, for example, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, triphenylamine, or the like. An aromatic ring group is preferred.

Specific examples of the n-valent aromatic ring group when n is an integer of 2 or more may preferably include (n-1) arbitrary hydrogen atoms in the specific example of the monovalent aromatic ring group. Base.

The n-valent aromatic ring group may further have a substituent.

Examples of the substituent which the n-valent aromatic ring group may have include an alkyl group, Cycloalkyl, aryl, amine, decyl, ureido, urethane, hydroxy, carboxy, halogen atom (except iodine atom), alkoxy, thioether, sulfhydryl, fluorenyloxy The carbon number of the substituent, the alkoxycarbonyl group, the cyano group, the nitro group or the like is preferably 8 or less.

Examples of the organic group containing at least one iodine atom represented by RI include an iodoalkyl group such as 2-iodoethyl or 3-iodopropyl.

As RI, an iodine atom is preferred.

n represents an integer of 1 or more. The upper limit of the integer represented by n is equal to the number of replaceable hydrogen atoms in the aromatic ring group represented by Ar ₂ .

n is preferably an integer of 2 or more, and more preferably an integer of 3 or more.

Specific examples of the low molecular compound (AD2) are shown below, but the present invention is not limited thereto.

[化47]

In the composition, the low molecular compound (AD2) may be used alone or in combination of two or more.

The content of the low molecular compound (AD2) in the composition is preferably from 0.1% by mass to 50% by mass, more preferably from 0.1% by mass to 30% by mass, based on the total solid content of the composition, and further preferably 1%. Mass%~10% by mass.

Next, the repeating unit (s) having a monovalent iodine atom which may be contained in the resin (AD1) will be described.

More specifically, the repeating unit (s) is a repeating unit containing a partial structure which does not escape by irradiation with actinic rays or radiation and has a monovalent iodine atom. That is, the repeating unit (s) contains a partial structure having a monovalent iodine atom (hereinafter also referred to as "partial structure (s1)"), and the partial structure (s1) is such that even an actinic ray is irradiated Or a part of the structure in which the radiation does not escape from the repeating unit (s). Even if the actinic ray or the radiation is irradiated, the partial structure (s1) having a monovalent iodine atom does not escape, and it is considered that the effect of light absorption is not reduced and high sensitivity can be obtained.

Here, a partial structure which is decomposed by irradiation of actinic rays or radiation will be described.

In the repeating unit (s) having a monovalent iodine atom, the partial structure (s1) having a monovalent iodine atom is preferably not contained in a partial structure which is decomposed by irradiation with actinic rays or radiation.

The partial structure which is decomposed by irradiation with actinic rays or radiation may, for example, be a partial structure represented by the following general formula (I) to formula (III). Further, by irradiation with actinic rays or radiation, the S atom-S atom bond in the general formula (I) of this paragraph is cleaved, and the O atom-N atom bond in the general formula (II) of this paragraph is cleaved. The O atom-N atom bond in the general formula (III) of the segment is cleaved.

In the general formulae (I) to (III) of the paragraph [0383], Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.

R ₂₀₆ , R ₂₀₇ and R ₂₀₈ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted extended alkenyl group or a substituted or unsubstituted extended aryl group.

Further, the repeating unit (s) having a monovalent iodine atom may also be a repeating unit having an acid-decomposable group. That is, in the repeating unit (s), the partial structure (s1) having a monovalent iodine atom is not excluded as a partial structure which is decomposed by the action of an acid and generates a polar group.

In this case, the resin (AD1) may contain only the repeating unit (s), and may not contain the repeating unit having the acid-decomposable group. In other words, in the resin (AD1) in this case, "a repeating unit having a partial structure which does not desorb by actinic radiation or radiation and has a monovalent iodine atom" also serves as "having decomposition by an action of an acid" And produces a repeating unit of a polar group."

As such a repeating unit (s), for example, a repeating unit represented by the following formula (1') can be preferably mentioned.

In the formula (1'), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ may be bonded to Ar ₁ to form a ring, and R _{13 in} this case represents an alkylene group.

X ₁ represents a single bond, an alkyl group, an aromatic ring group, -O-, -S-, -CO-, -COO-, -SO ₂ NH-, -SO ₂ O-, -NR- (R is a hydrogen atom) Or an alkyl group, a divalent nitrogen-containing non-aromatic heterocyclic group, or a divalent linking group comprising such a combination.

Ar ₁ represents an aromatic ring group.

RI represents an iodine atom or an organic group containing at least one iodine atom.

n represents an integer of 1 or more.

In the formula (1'), as the alkyl group represented by R ₁₁ to R ₁₃ , a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a second group which may have a substituent may be mentioned. An alkyl group having a carbon number of 20 or less, such as a butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having a carbon number of 8 or less, and particularly preferably an alkyl group having 3 or less carbon atoms. .

The alkyl group contained in the alkoxycarbonyl group is preferably the same alkyl group as the alkyl group in the above R ₁₁ to R ₁₃ .

The cycloalkyl group may be a monocyclic type or a polycyclic type. A monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group which may have a substituent is preferable.

Examples of the halogen atom include halogen atoms other than the iodine atom.

When R ₁₃ is bonded to Ar ₁ to form a ring, examples of the alkylene group include a methylene group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a octyl group. The alkyl group is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms.

The alkylene group represented by X ₁ may, for example, be an alkylene group having a carbon number of 1 to 8 such as a methylene group, an ethyl group, a propyl group, a butyl group, a hexyl group or a octyl group, and preferably a carbon group. The alkyl group having 1 to 4 is more preferably an alkyl group having 1 to 2 carbon atoms.

The aromatic ring group represented by X ₁ is a divalent aromatic ring group, and examples thereof include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, and a 1,4-naphthyl group. And, preferably, it is a 1,4-phenylene group.

The alkyl group represented by R in -NR- represented by X ₁ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a second butyl group or a hexyl group which may have a substituent. An alkyl group having 20 or less carbon atoms such as 2-ethylhexyl, octyl or dodecyl group is preferably an alkyl group having 8 or less carbon atoms.

The divalent nitrogen-containing non-aromatic heterocyclic group represented by X ₁ may, for example, be a group obtained by removing two arbitrary hydrogen atoms from a hetero ring such as pyrrole, pyrrolidine or piperidine.

Among these, as X ₁ , a single bond, -COO-, -NR-, and a divalent linking group containing a combination of these groups are preferable, and -COO- is more preferable.

The aromatic ring group represented by Ar ₁ is an (n+1)-valent aromatic ring group.

Examples of the divalent aromatic ring group in the case where n is 1 include a aryl group having 6 to 18 carbon atoms such as a phenylene group, a methylphenyl group, an anthranyl group, and a fluorenyl group, or a thiophene or a furan group. A heterocyclic aromatic ring group of pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole or thiazole is preferred.

Specificity of the (n+1)-valent aromatic ring group when n is an integer of 2 or more For example, a group obtained by removing (n-1) arbitrary hydrogen atoms from the specific example of the divalent aromatic ring group is preferably mentioned.

The (n+1)-valent aromatic ring group may further have a substituent.

Examples of the substituent which the (n+1)-valent aromatic ring group may have include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, and a carboxyl group. Further, a halogen atom (excluding an iodine atom), an alkoxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group or a nitro group, and the number of carbon atoms of the substituent is preferably 8 or less.

The aromatic ring group represented by Ar ₁ is preferably a group in which a phenyl group, a naphthyl group, and (n-1) arbitrary hydrogen atoms are removed from the groups.

Examples of the organic group containing at least one iodine atom represented by RI include an iodoalkyl group such as 2-iodoethyl or 3-iodopropyl.

As RI, an iodine atom is preferred.

n represents an integer of 1 or more. The upper limit of the integer represented by n is equal to the number of replaceable hydrogen atoms in the aromatic ring group represented by Ar ₁ .

The reason why n is a higher sensitivity and a high resolution is preferably an integer of 2 or more, and more preferably an integer of 3 or more.

Specific examples of the repeating unit (s) having a monovalent iodine atom are shown below, but the present invention is not limited thereto.

[化50]

[化51]

In the resin (AD1), the repeating unit (s) may be used alone or in combination of two or more.

The content of the repeating unit (s) in the resin (AD1) (which is a total when it is contained) is preferably from 0.1 mol% to 80 mol%, relative to all the repeating units in the resin (AD1). Good for 0.1 mol%%~50 mol%, and then better for 1 Mo Ear %~30% of the ear.

[7] Resist solvent

The solvent which can be used for the preparation of the composition is not particularly limited as long as it is a solvent for dissolving each component, and examples thereof include an alkanediol monoalkyl ether carboxylate (PGMEA (propylene glycol). Monomethyl ether acetate); 1-methoxy-2-ethoxypropane propane), alkanediol monomethyl ether (PGME (propylene glycol monomethyl ether); 1-methoxy-2) -propanol), etc., alkyl lactate (ethyl lactate, methyl lactate, etc.), cyclic lactone (γ-butyrolactone, etc., preferably having a carbon number of 4 to 10), chain or cyclic a ketone (2-heptanone, cyclohexanone, etc., preferably having a carbon number of 4 to 10), an alkyl carbonate (ethyl carbonate, propyl carbonate, etc.), an alkyl carboxylate (preferably acetic acid) An alkyl acetate such as butyl ester or the like, an alkyl alkoxyacetate (ethyl ethoxypropionate) or the like. Examples of other usable solvents include, for example, the solvent described in [0244] of the specification of U.S. Patent Application Publication No. 2008/0248425 A1.

Among the above, an alkanediol monoalkyl ether carboxylate and an alkanediol monoalkyl ether are preferred.

These solvents may be used singly or in combination of two or more. When two or more kinds are mixed, it is preferred to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.

The solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and as the solvent having no hydroxyl group, an alkanediol monoalkyl ether carboxylate is preferred.

The amount of the solvent used in the total amount of the composition of the present invention can be appropriately adjusted depending on the desired film thickness, etc., and generally the total solid content concentration of the composition is from 0.5% by mass to 5% by mass, preferably 0.8% by mass. The adjustment is performed in a manner of 3 mass%, more preferably 0.8 mass% to 2 mass%, and further preferably 0.8 mass% to 1.5 mass%.

[8] Other additives

The composition of the present invention may contain, in addition to the components described above, a carboxylic acid sulfonium salt, a proceeding of SPIE, a solubilization preventing molecular weight of 3000 or less as described in 2724, 355 (1996), and the like. Compounds, dyes, plasticizers, photosensitizers, light absorbers, antioxidants, and the like.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples.

<Synthesis Example 1: Synthesis of Polymer Compound (P-1)>

30 g of poly(p-hydroxystyrene) (VP-2500, manufactured by Nippon Soda Co., Ltd.) as a polyhydroxystyrene compound was dissolved in 120 g of PGMEA (propylene glycol monomethyl ether acetate). To the solution, 10.40 g of 2-cyclohexylethyl vinyl ether as a vinyl ether compound and 1.45 g of 2 mass% camphorsulfonic acid (PGMEA solution) were added, and the mixture was stirred at room temperature for 2 hours. 1.05 g of 10% by mass of triethylamine (PGMEA solution) was added, and after stirring briefly, the reaction liquid was transferred to a separatory funnel containing 165 mL of ethyl acetate. After the organic layer was washed three times with 200 mL of distilled water, ethyl acetate was removed by an evaporator. The resulting reaction droplets were added to 2 L of hexane and the supernatant was removed. The obtained product was dissolved in PGMEA 95g under reduced pressure The low-boiling solvent was removed, whereby 132.3 g of a PGMEA solution (28.3% by mass) of the polymer compound (P-1) was obtained.

With respect to the polymer compound (P-1), the molar ratio of each repeating unit was determined using nuclear magnetic resonance (NMR) hydrogen spectroscopy ( ¹ H-NMR) and nuclear magnetic resonance carbon spectroscopy ( ¹³ C-NMR). Further, the mass average molecular weight (Mw) and the degree of dispersion (Mw/Mn) in terms of polystyrene were determined by using GPC (solvent: THF). The results are shown in Table 1 below. In the table, the molar ratio of each repeating unit is described in the "composition ratio" row (corresponding to the order from the left side).

<Synthesis Example 2: Synthesis of Polymer Compound (P-2)>

25.5 g of p-hydroxystyrene (53.1 mass% of a propylene glycol monomethyl ether solution), 16.0 g of a compound represented by the following formula (X), and 2.42 g of a polymerization initiator V-601 (Wako Pure Chemical Industries, Ltd.) (manufactured by the company) dissolved in 31.4 g of propylene glycol monomethyl ether (PGME). 10.8 g of PGME was added to the reaction solution, and it was added dropwise to a system of 85 ° C for 2 hours under a nitrogen atmosphere. The reaction solution was heated and stirred for 4 hours, and then allowed to cool to room temperature.

The reaction solution was diluted by adding 33 g of acetone. Will be diluted The solution was added dropwise to 1000 g of heptane/ethyl acetate (mass ratio) = 8/2, and the polymer was precipitated and filtered. Thereafter, the solid was dried under reduced pressure to obtain 36.32 g of a polymer compound (P-2).

In Table 1, another polymer compound (P-3) to a polymer compound (P-10) was synthesized by the same method as the polymer compound (P-1) or the polymer compound (P-2).

Polymer-X1 was synthesized using p-ethoxylated styrene and a third butyl methacrylate by a known radical polymerization method.

[Table 1-1]

[Composition 1~ Composition 11]

Each component shown in the following Table 2 was dissolved in the solvent shown in the table. It was filtered using a polyethylene filter having a pore diameter of 0.1 μm.

[Table 2]

The details of each component other than the polymer compound (A) shown in Table 2 are shown below. <acid generator (B)>

[化53]

<Basic compound> TBAH: tetrabutylammonium hydroxide DBN: 1,5-diazabicyclo[4.3.0]non-5-ene TDA: tri-n-decylamine <surfactant>W-1: Meijia Method (Megafac) F176 (manufactured by Diane Health (DIC) Co., Ltd.) W-2: PF6320 (manufactured by OMNOVA) <solvent> PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether EL : ethyl lactate

<EB exposure: Example 1 to Example 9, Comparative Example 1 to Comparative Example 3>

The composition 1 to the composition 11 described in Table 2 were used, and a resist pattern was formed by the following operation. The details of the resist pattern forming conditions are shown in Table 3.

[resist coating and prebaking (PB)]

The prepared positive resist solution was uniformly coated on a ruthenium substrate subjected to hexamethyldiazane treatment using a spin coater. Next, heating and drying were performed at 120 ° C for 90 seconds using a hot plate.

〔exposure〕

For the resist film, an electron beam irradiation device (JBX6000 manufactured by Japan Electron Optics Laboratory (JEOL); acceleration voltage 50 KeV) was used, and a line pattern having a line width of 20 nm was used in units of 2.5 nm. (The length direction is 0.5 mm, the number of roots is 40) The exposure amount is changed to perform exposure.

[exposure after exposure (PEB)]

Immediately after the exposure, the film was heated at 110 ° C for 90 seconds on a hot plate.

〔development〕

Spray development

Using a shower-type developing device (ADE3000S manufactured by ACTES Co., Ltd.), the wafer was rotated at 50 revolutions (rpm) while the alkalinity shown in Table 3 was used at a flow rate of 200 mL/min. The developing solution (23 ° C) was sprayed and sprayed out for the time shown in Table 3 to carry out development.

Thereafter, while the wafer was rotated at 50 revolutions (rpm), pure water was used as the eluent (23 ° C), and sprayed at a flow rate of 200 mL/min for 30 seconds to carry out a rinsing treatment.

Finally, the wafer was dried by rotating at a high speed of 60 seconds at 2500 revolutions (rpm).

2. Liquid coating development

The alkali development described in Table 3 was carried out at a flow rate of 200 mL/min while rotating the wafer at 50 revolutions (rpm) using a shower-type developing device (ADE3000S manufactured by ACTES Co., Ltd.). Liquid (23 ° C) spray sprayed for 5 seconds, and The developer is deposited on the wafer. Subsequently, the rotation of the wafer was stopped, and the wafer was allowed to stand for the time described in Table 3 for development.

Thereafter, while the wafer was rotated at 50 revolutions (rpm), pure water was used as the eluent (23 ° C), and sprayed at a flow rate of 200 mL/min for 30 seconds to carry out a rinsing treatment.

In Table 3, the addition amount described in the column of other additives is a value expressed by mass% with respect to the total mass of the alkaline developer.

The evaluation of the resist pattern was performed on the following items. The details of the results are shown in Table 4.

[Line Edge Roughness (LER)]

For any 30 points in the longitudinal direction of 1 μm of the line pattern having a line width of 20 nm, a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) was used to measure the distance from the reference line which should be located at the edge, and the standard deviation was obtained. , thereby calculating 3σ. The smaller the value, the better the line edge roughness.

[CDU]

Using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), the dimensions of 50 lines were measured at a line width of 20 nm at intervals of 2 mm, and the standard deviation of 50 parts was determined. Calculated as 3σ. The smaller the value, the better the uniformity of the line width and the better the performance.

[EL]

The exposure amount of the line and space pattern in which the line width is 20 nm is set as the optimum exposure amount, and the exposure amount range in which the line width of 20 nm±10% is reproduced is divided by the optimum exposure amount in percentage (%). value. The larger the value, the less the line width variation with respect to the change in exposure amount (the greater the latitude), the better the performance.

According to the results shown in Table 4, the resist pattern forming method of the present invention can simultaneously satisfy good CDU, small line edge roughness (LER), and large exposure latitude (EL).

<EUV exposure: Example 10 to Example 18, Comparative Example 4 to Comparative Example 6>

A resist pattern was formed by performing the same operation as the EB exposure, using EUV light (wavelength 13 nm) and exposing using a 1:1 line having a line width of 24 nm and a space mask pattern. Evaluation. The pattern formation conditions are shown in Table 5, and the pattern evaluation results are shown in Table 6.

According to the results shown in Table 6, the resist pattern forming method of the present invention can simultaneously satisfy a good CDU, a small line edge roughness (LER), and the like when EUV light (wavelength 13 nm) is used. Large exposure latitude (EL).

Claims (19)

A pattern forming method comprising: a step of applying a sensitizing ray-sensitive or radiation-sensitive resin composition onto a substrate to form a sensitized ray-sensitive or radiation-sensitive film; and the sensitizing ray-sensitive or radiation-sensitive film a step of performing exposure; and a step of developing the exposed sensitizing ray-sensitive or radiation-sensitive film using an alkali developing solution, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition contains (A) a polymer compound comprising a repeating unit represented by the following formula (I), wherein a concentration of an alkaline component in the alkaline developing solution is 1.25 mass% to 2.2 mass%, and the sensitizing ray or radiation is irradiated The film thickness of the film is 60 nm or less. In the formula (I), R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; R ₀₃ may be bonded to Ar ₁ to form Ring, where R ₀₃ represents an alkylene group; Ar ₁ represents an (n+1)-valent aromatic ring group, and when bonded to R ₀₃ to form a ring, represents an (n+2)-valent aromatic ring group; Each of Y represents independently a hydrogen atom or a group which is desorbed by the action of an acid; wherein at least one of Y represents a group which is desorbed by the action of an acid; and n represents an integer of 1 to 5. The pattern forming method according to claim 1, wherein the alkaline developing solution is an aqueous solution containing tetramethylammonium hydroxide. The pattern forming method according to claim 2, wherein the alkaline developing solution contains an alcohol. The pattern forming method according to claim 2, wherein the alkaline developing solution contains a surfactant. The pattern forming method according to claim 2, wherein the exposure in the exposing step is performed by electron beam or extreme ultraviolet light. The pattern forming method according to claim 2, wherein in the formula (I), at least one Y is a group represented by the following formula (II), Wherein L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; M represents a single bond or a divalent linking group; and Q represents an alkyl group, a cycloalkyl group, or an aromatic group; a group, an amine group, an ammonium group, a thiol group, a cyano group or an aldehyde group; the cycloalkyl group and the aryl group may contain a hetero atom; at least two of Q, M, and L ₁ may be bonded to each other to form a ring. The pattern forming method according to claim 6, wherein at least one of L ₁ and L ₂ in the formula (II) is a tertiary carbon atom or a quaternary carbon atom adjacent to a carbon atom in the formula atom. The pattern forming method according to claim 2, wherein in the formula (I), at least one Y is a group represented by the following formula (III), Wherein L ₃ , L ₄ and L ₅ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; wherein, L ₃ , L ₄ and L ₅ are not all hydrogen atoms; The cycloalkyl group and the aryl group may contain a hetero atom; at least two of L ₃ , L ₄ and L ₅ may be bonded to each other to form a ring. The pattern forming method according to claim 2, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains (B) a compound which generates an acid by irradiation with actinic rays or radiation. The pattern forming method according to claim 1, wherein the sensitized ray-sensitive or radiation-sensitive film has a film thickness of 15 nm to 50 nm. The pattern forming method according to claim 1, wherein the sensitized ray-sensitive or radiation-sensitive film has a film thickness of 15 nm to 40 nm. A pattern formed by the pattern forming method according to claim 9 of the patent application. A resin composition having a sensitizing ray property or a radiation sensation, and the resin composition is used in the pattern forming method according to claim 9 of the patent application. A film having a sensitizing ray or a radiation sensation formed using the resin composition as described in claim 13 of the patent application. A blank mask comprising the film of claim 14 of the patent application. A method of manufacturing a reticle comprising the pattern forming method according to claim 9 of the patent application. A reticle manufactured by the method of manufacturing a reticle according to claim 16 of the patent application. A method for producing a mold for nanoimprint, which comprises the pattern forming method according to claim 9 of the patent application. A mold for nanoimprinting, which is produced by the method for producing a mold for nanoimprinting according to claim 18 of the patent application.