JP6387403B2 - Pattern forming method, photomask manufacturing method, and nanoimprint mold manufacturing method - Google Patents

Description

  The present invention uses electron beams (EB), extreme ultraviolet rays (EUV), etc., which are preferably used in ultra-microlithography processes such as the manufacture of VLSI and high-capacity microchips, and other photofabrication processes. Pattern forming method, pattern, actinic ray sensitive or radiation sensitive resin composition, actinic ray sensitive or radiation sensitive film, and mask blank provided with actinic ray sensitive or radiation sensitive film About.

  The pattern forming method of the present invention can also be suitably applied to a photomask manufacturing method and a nanoimprint mold manufacturing method. The present invention also relates to a photomask manufacturing method, a photomask, a nanoimprint mold manufacturing method, and a nanoimprint mold.

  In microfabrication using a resist composition, with the high integration of integrated circuits, in recent years, ultrafine (for example, 1: 1 line and space with a line width of 25 nm or less) is required to be formed.

  For this reason, there has been a trend toward shorter exposure wavelengths, such as from g-line to i-line and further to excimer laser light. At present, development of lithography technology using extreme ultraviolet light (EUV) and electron beams is progressing. It is out. In recent years, it has also been used for mold making applications used in so-called imprint processes (for example, Patent Document 1).

  Further, with the miniaturization of the pattern to be formed, the control of the line width becomes more difficult, and the problem that the uniformity of the line width within the wafer surface (Critical Dimension Uniformity; hereinafter abbreviated as CDU) deteriorates. doing. In order to prevent this problem, the resist has been improved, but it is not sufficient, and there is a concern that the yield at the time of forming an integrated circuit will deteriorate. In addition, with the miniaturization of the line width, it has become difficult to suppress line width variation (also referred to as exposure margin, hereinafter referred to as EL (Exposure Latitude)) with respect to the exposure amount, and improvement is required.

  Resist compositions used for lithography using extreme ultraviolet light (EUV) and electron beams, and for imprint mold production, for example, replacing hydrogen atoms of phenolic hydroxyl groups with acid labile groups such as acetal structures For example, Patent Documents 2 to 4 disclose a resin using the prepared resin.

  As an alkaline developer used in the positive chemical amplification image forming method, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (hereinafter abbreviated as TMAH aqueous solution) is used as an industry standard developer. However, with the miniaturization of the pattern described above, there is a problem of deterioration of line edge roughness (LER) due to a reduction in the thickness of the resist film during development.

  In order to solve this problem, for example, when developing a positive novolak resist, a method of developing a pattern using an alkaline developer of 0.115N to 0.15N (for example, Patent Document 5), or 1.2 A method of developing a resist film formed from a resist composition containing a resin having an ester-type acid-decomposable repeating unit using a TMAH aqueous solution having a mass% or less (for example, Patent Document 6), and 0.5-1. A method of developing a resist film formed from a resist composition containing a resin having a repeating unit in which a hydrogen atom of a phenolic hydroxyl group is substituted with an acid leaving group using a 1 mass% TMAH aqueous solution (for example, Patent Document 7) ) Etc. have been proposed.

JP 2008-162101 A JP 2000-239538 A JP 2006-146242 A International Publication No. 05/023880 JP-A-63-232430 JP 2010-134240 A JP 2013-44809 A

  However, in any combination of existing resist composition, developer, rinse solution, etc., the line width uniformity (CDU), exposure margin (EL), and good line edge roughness (LER) of ultra fine pattern are satisfied. The current situation is not done.

  An object of the present invention is to provide an ultrafine pattern having a wide exposure margin (EL), a small line edge roughness (LER), a good line width uniformity (CDU), for example, a line width of 25 nm or less. A pattern forming method, a pattern, an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, and a mask blank provided with the actinic ray-sensitive or radiation-sensitive film .

  Moreover, the objective of this invention is providing the manufacturing method of the photomask including the said pattern formation method, the manufacturing method of the mold for nanoimprint, a photomask, and the mold for nanoimprint.

As a result of intensive studies, the present inventors have pattern-exposed an actinic ray-sensitive or radiation-sensitive film formed using an actinic ray-sensitive or radiation-sensitive resin composition containing a polymer compound having a specific structure, It has been found that the above object can be achieved by developing with an alkali developer having a specific alkali component concentration.
That is, this invention is as follows in one aspect | mode.

[1] a step of applying an actinic ray-sensitive or radiation-sensitive resin composition on a substrate to form an actinic ray-sensitive or radiation-sensitive film;
-A step of exposing the actinic ray-sensitive or radiation-sensitive film; and-a pattern forming method comprising a step of developing the actinic-ray-sensitive or radiation-sensitive film after exposure using an alkali developer.
The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a polymer compound containing a repeating unit represented by the following general formula (I),
The pattern formation method whose density | concentration of the alkali component in the said alkali developing solution is 1.25 mass%-2.2 mass%.

In general formula (I), R ₀₁ , R ₀₂ and R ₀₃ each independently represents 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, in which case 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.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 5.

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

  [3] The pattern forming method according to [1] or [2], wherein the alkali developer contains an alcohol.

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

  [5] The pattern forming method according to any one of [1] to [4], wherein the exposure in the exposure step is performed with an electron beam or EUV light.

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

In the formula, 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 amino group, an ammonium group, a mercapto 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], in which at least one of L ₁ and L _{2 in} the general formula (II) is a tertiary or quaternary carbon atom adjacent to the carbon atom in the formula.

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

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. However, not all of L ₃ , L ₄ and L ₅ are hydrogen atoms. The cycloalkyl 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] Any one of [1] to [8], wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains (B) a compound that generates an acid upon irradiation with actinic rays or radiation. The pattern forming method according to 1.

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

  [11] An actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method according to any one of [1] to [9].

  [12] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to [11].

  [13] A mask blank provided with the actinic ray-sensitive or radiation-sensitive film according to [12].

  [14] A photomask manufacturing method including the pattern forming method according to any one of [1] to [9].

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

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

  [17] A nanoimprint mold manufactured by the method for manufacturing a nanoimprint mold according to [16].

  According to the present invention, there is provided a pattern forming method capable of forming an ultrafine pattern having, for example, a line width of 25 nm or less, with excellent EL, LER, and CDU, and excellent developability and productivity. The manufacturing method of the photomask containing the method and the manufacturing method of the mold for nanoimprint can be provided. Further, according to the present invention, there is provided an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, an actinic ray-sensitive or radiation-sensitive film suitably used for the pattern forming method. The provided mask blanks can be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
Specifically, the resist pattern forming method of the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution or non-substitution includes what has a substituent with what does not have a substituent. 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, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, “light” means actinic rays or radiation.

  Unless otherwise specified, “exposure” in this specification is not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays and EUV light, but also drawing with electron beams and ion beams. Are also included in the exposure.

[Pattern formation method]
The pattern forming method of the present invention comprises:
A step of forming an actinic ray sensitive or radiation sensitive film by applying an actinic ray sensitive or radiation sensitive resin composition on a substrate (film forming step);
A step of exposing the actinic ray-sensitive or radiation-sensitive film, and a step of developing the actinic-ray-sensitive or radiation-sensitive film after exposure using an alkali developer.
The pattern forming method of the present invention is an actinic ray-sensitive or radiation-sensitive resin containing a polymer compound having a repeating unit represented by the general formula (I) described later as the actinic ray-sensitive or radiation-sensitive resin composition. One of the features is that an alkaline developer having a concentration of an alkaline component of 1.25% by mass to 2.2% by mass is used as the alkaline developer.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is preferably a chemically amplified actinic ray-sensitive or radiation-sensitive resin composition.
The resist pattern of the present invention is formed by the resist pattern forming method of the present invention.

  The present invention also relates to an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “the composition of the present invention”) used in the resist pattern forming method of the present invention, as will be described later. .

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

<Film forming process>
In the film-forming process for forming the actinic ray-sensitive or radiation-sensitive film, the actinic ray-sensitive or radiation-sensitive resin composition is filtered as necessary and then applied onto a support (substrate). The filter is preferably 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 an application method of the actinic ray-sensitive or radiation-sensitive resin composition on the support (substrate), an appropriate application method such as a spinner can be used. As the substrate, a substrate (eg, silicon, silicon dioxide coating) used for manufacturing an integrated circuit element can be used. If necessary, various base films (inorganic films, organic films) can be applied between the actinic ray-sensitive or radiation-sensitive film and the substrate.

  In the present invention, in order to resolve an ultrafine pattern such as a 1: 1 line and space pattern having a line width of 25 nm or less, the actinic ray-sensitive or radiation-sensitive film thickness may be 60 nm or less. preferable. By making the film thickness 60 nm or less, the aspect ratio of the pattern becomes small, and the pattern collapse hardly occurs. The range of the film thickness is preferably 15 nm to 60 nm. The film thickness of 15 nm or more is preferable because good etching resistance can be obtained. The range of the film thickness is more preferably 15 to 50 nm, and particularly preferably 15 to 40 nm. When the film thickness is in this range, excellent etching resistance and resolution performance can be satisfied at the same time.

<Exposure process>
The actinic ray-sensitive or radiation-sensitive film thus formed is irradiated with actinic rays or radiation through a predetermined mask. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.
Although it does not specifically limit as actinic light or a radiation, For example, they are KrF excimer laser, ArF excimer laser, EUV light, an electron beam, etc., EUV light and an electron beam are preferable.

<Bake process>
The pattern forming method of the present invention may include a baking (heating) step, and may further include a baking step a plurality of times.
In one embodiment, the pattern forming method of the present invention preferably includes a baking process (referred to as pre-baking, hereinafter abbreviated as “PB”) after film formation and before exposure. PB temperature becomes like this. Preferably it is 60 to 150 degreeC, More preferably, it is 80 to 140 degreeC. The PEB time is preferably 60 to 1200 seconds, more preferably 60 to 600 seconds.

  PB can be performed by means provided in a normal exposure / development machine, and may be performed using a hot plate or the like.

  In another embodiment, the pattern forming method of the present invention preferably includes a baking process (hereinafter referred to as “post exposure baking”, hereinafter abbreviated as “PEB”) after exposure and before development.

PEB temperature becomes like this. Preferably it is 80-150 degreeC, More preferably, it is 90-150 degreeC, More preferably, it is 100-140 degreeC.
The PEB time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.
PEB can be performed by means provided in a normal exposure / development machine, and may be performed using a hot plate or the like.
PEB promotes the reaction in the exposed area and improves CDU and LER.

<Alkali development process>
The density | concentration of the alkali component of an alkali developing solution is 1.25 mass%-2.2 mass% with respect to the total mass of an alkali developing solution. CDU improves by making the density | concentration of an alkali component into the said range. The reason for this is not clear, but by setting the concentration of the alkali component in the above range, the alkali component is deactivated by carbon dioxide in the atmosphere, and the component concentration varies locally within the wafer surface. It is considered that the influence that the line width fluctuates can be suppressed, and the line width fluctuation due to the film reduction of the unexposed portion of the resist film can be suppressed at the same time.

  In addition, when the actinic ray-sensitive or radiation-sensitive resin composition containing the polymer compound having the repeating unit represented by the general formula (I) described later and the alkali component concentration within the above range is used Simultaneously with the improvement of CDU, LER and EL are improved, and the resolution performance is improved. The reason for this is not clear, but the pattern edge film is suppressed by suppressing the decrease in the unexposed area of the actinic ray-sensitive or radiation-sensitive film by combining the alkali component concentration in the alkali developer and the polymer compound. It can be considered that the occurrence of edge roughness due to roughness can be suppressed, and the variation in line width due to the decrease in film thickness due to the reduction in film thickness can be suppressed.

  In one embodiment of the present invention, the alkali component concentration in the alkali developer is preferably from 1.25% by mass to 2.0% by mass, and more preferably from 1.35% by mass to 1.8% by mass. preferable.

  Examples of the alkali component in the alkali developer used (hereinafter also referred to as “alkaline species”) include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, and ethylamine. Primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydride Tetraalkylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, such as oxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide And alkaline species such as quaternary ammonium salts such as triethylbenzylammonium hydroxide and cyclic amines such as pyrrole and pihelidine, and aqueous solutions of these alkali species can be used as the alkaline developer.

  Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant (for example, Surfinol 440, 465 (Nisshin Chemical Industry Co., Ltd.)) is added to the alkaline aqueous solution, thereby increasing the surface tension. A reduced alkaline aqueous solution can also be used. By reducing the surface tension, the wettability of the developer with respect to the wafer is improved and the CDU is improved.

  The surfactants such as alcohols and nonionic surfactants may be added in a necessary amount that sufficiently reduces the surface tension of the alkaline developer.

  Since the relationship between the amount of alcohol or surfactant added and the surface tension of the aqueous solution varies depending on the type of compound to be added, the amount added cannot be generally specified, but for example, when isopropyl alcohol is added. Can reduce the surface tension of the alkali developer to 30 to 50 mN / m by adding 5 to 20% by mass with respect to the total mass of the alkali developer.

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

Of the alkali species in these developers, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide is more preferred.
In addition, it is preferable that the alkali developer does not contain metal ions and halogen ions, and ideally each has 0 mass ppb, but excludes the case where it is contained in a trace amount as long as the effect of the present invention is not impaired. Not what you want. The metal ion content 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 in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer application nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) , Shower developing method) and the like can be applied.

  Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.

  A particularly preferred developing method is a method in which a substantially fresh alkaline developer is continuously supplied for development, and specifically, a method in which a substantially fresh alkaline developer is continuously sprayed on the substrate surface (spray). Or a method in which a substantially fresh alkali developer is continuously applied while scanning a developer application nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method). By continuously supplying and developing a substantially fresh alkaline developer, development in the exposed portion proceeds rapidly, and resolution performance is improved. In addition, by continuously supplying a fresh alkali developer and developing, it is possible to reduce residual development defects generated at the stage of switching from development to rinsing.

  It is important that the development time can be compatible with the productivity and the time during which the components in the actinic ray-sensitive or radiation-sensitive resin composition in the exposed area are sufficiently dissolved. Since the development time varies depending on the concentration of alkali species contained in the developer and the alkali solubility of the components in the actinic ray-sensitive or radiation-sensitive resin composition, it cannot be uniquely determined.

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

<Rinse process>
In one embodiment, the pattern forming method of the present invention preferably includes a rinsing step of stopping development while substituting with pure water after the step of developing.
In the rinsing step, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the pure water.
The rinsing time is preferably a time during which the alkaline developer on the substrate is sufficiently washed away, and is usually preferably 5 seconds to 600 seconds. More preferably, it is 10 seconds-300 seconds.
The temperature of the rinse liquid is preferably 0 ° C to 50 ° C, and more preferably 10 ° C to 30 ° C.

  Furthermore, the present invention provides a nanoimprint mold manufactured by the method for manufacturing a nanoimprint mold including the pattern forming method of the present invention, and a photomask manufactured by the method of manufacturing a photomask including the pattern forming method of the present invention. Also related.

  Such a nanoimprint mold and a photomask are obtained by using a mask blank provided with an actinic ray-sensitive or radiation-sensitive film obtained from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Preferably it is manufactured.

  When a pattern is formed on a mask blank having such an actinic ray-sensitive or radiation-sensitive film based on the pattern forming method of the present invention, the substrate used is transparent such as quartz or calcium fluoride. A substrate can be mentioned. In general, a light-shielding film, an antireflection film, a phase shift film, and additional functional films such as an etching stopper film and an etching mask film are laminated on the substrate. As a material for the functional film, a film containing a transition metal such as silicon or chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium is laminated. In addition, as a material used for the outermost layer, silicon or a material containing oxygen and / or nitrogen in silicon as a main constituent material, and further a silicon compound material containing a transition metal-containing material as a main constituent material Or a transition metal, in particular, one or more selected from chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium, etc., or a material further containing one or more elements selected from oxygen, nitrogen, and carbon The transition metal compound material is exemplified.

  The light shielding film may be a single layer, but more preferably has a multilayer structure in which a plurality of materials are applied. In the case of a multilayer structure, the thickness of the film per layer is not particularly limited, but is preferably 5 nm to 100 nm, and more preferably 10 nm to 80 nm. Although it does not specifically limit as thickness of the whole light shielding film, It is preferable that it is 5 nm-200 nm, and it is more preferable that it is 10 nm-150 nm.

  Next, the actinic ray-sensitive or radiation-sensitive film is exposed and developed as described above to obtain a pattern. And using this pattern as a mask, an etching process etc. are performed suitably and a nanoimprint mold and a photomask are manufactured.

  The photomask in the present invention may be a light transmissive mask used in an ArF excimer laser or the like, or a light reflective mask used in reflective lithography using EUV light as a light source.

  In addition, about the process in the case of producing the mold for imprints using the composition of this invention, patent 4109085 gazette, Unexamined-Japanese-Patent No. 2008-162101, and "the foundation of nanoimprint, technical development, and application development, for example" -Nanoimprint substrate technology and latest technology development-edited by Yoshihiko Hirai (Frontier Publishing) ".

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

  Further, the pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.

[Actinic ray-sensitive or radiation-sensitive resin composition]
Below, the actinic-ray sensitive or radiation sensitive resin composition of this invention used for the pattern formation method of this invention is demonstrated in detail.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a polymer compound having a repeating unit represented by the general formula (I) described later.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a compound that generates an acid upon irradiation with actinic rays or radiation, and a basic compound.

[1] Polymer Compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a polymer compound having a repeating unit represented by the following general formula (I) (hereinafter referred to as “polymer compound (A)”). Contain). When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light (for example, EUV) having a wavelength of 50 nm or less, the polymer compound (A) is further substituted with hydroxystyrene. It is preferable to have a repeating unit. Here, as hydroxystyrene, p-hydroxystyrene is preferable.

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

In general formula (I), R ₀₁ , R ₀₂ and R ₀₃ each independently represents 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, in which case 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.

  n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.

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

The alkyl group as R _{01 to} R ₀₃ is, for example, an alkyl group having 20 or less carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a hexyl group. , 2-ethylhexyl group, octyl group or dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. In addition, these alkyl groups may have a substituent.

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

  The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Preferably, a C3-C8 monocyclic cycloalkyl group, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is mentioned. In addition, these cycloalkyl groups may have a substituent.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.

When R ₀₃ represents an alkylene group, the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.

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

The (n + 1) -valent aromatic ring group as Ar ₁ preferably has 6 to 14 carbon atoms. Examples of the divalent aromatic ring group when n is 1 include a phenylene group, a tolylene group, and a naphthylene group.

  Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.

  In addition, these aromatic ring groups may further have a substituent.

Examples of the group Y leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ). _{), - C (R 1)} (R 2) (OR 39), - C (R 1) (R 2) -C (= O) -O-C (R 36) (R 37) (R 38), And a group represented by —CH (R ₃₆ ) (Ar).

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring structure.
R ₁ and R ₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl 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. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- A butyl group, a hexyl group, and an octyl group are mentioned.

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. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, A tetracyclododecyl group and an androstanyl group are mentioned. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group as 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 anthryl group.

The aralkyl group as R _{36 to} R ₃₉ , R ₁ , or R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and for example, a benzyl group, a phenethyl group, and a naphthylmethyl group are preferable.

The alkenyl group as 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 that R ₃₆ and R ₃₇ may be bonded to each other may be monocyclic or polycyclic. 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. As the polycyclic type, a cycloalkane structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. Note that some of the carbon atoms in the ring structure may be substituted with a heteroatom such as an oxygen atom.

  Each of the above groups may have a substituent. Examples of this substituent include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, and acyloxy groups. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.

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

In general 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 amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. In addition, these cycloalkyl groups and aryl groups may contain a hetero atom.
Note that 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 specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and An octyl group is mentioned.

The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples 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 specifically includes a phenyl group, a tolyl group, a naphthyl group, and an anthryl 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 include a benzyl group and a phenethyl group.

L ₁ and L ₂ each independently preferably represent a hydrogen atom, an alkyl group or a cycloalkyl group. L ₁ is more preferably a hydrogen atom. L ₂ is more preferably an alkyl group or a cycloalkyl group, and in this alkyl group and cycloalkyl group, the atom adjacent to the carbon atom in the general formula (II) is a tertiary or quaternary carbon atom. Is more preferable, and a quaternary carbon atom is particularly preferable.

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 ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene group. (Preferably a cycloalkylene group having 3 to 15 carbon atoms, such as a cyclopentylene group or a cyclohexylene group), an alkenylene group (preferably an alkenylene group having 2 to 8 carbon atoms, such as an ethylene group, a propenylene group or a butenylene group) , an arylene group (preferably an arylene group having 6 to 20 carbon atoms, such as phenylene group, tolylene group or a naphthylene group), - S -, - O -, - CO -, - SO 2 -, - N (R 0) -Or a combination of two or more thereof. 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 specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. Can be mentioned.

  M preferably represents a single bond, or a divalent linking group composed of an alkylene group, —O—, or a combination thereof, and more preferably represents a single bond, an alkylene group, or an alkyleneoxy group.

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

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

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

Examples of the ring structure that 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 these form a propylene group or a butylene group. This 5-membered or 6-membered ring structure contains an oxygen atom.

Each group represented by L ₁ , L ₂ , M and Q in the general formula (II) may have a substituent. Examples of this substituent include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, and acyloxy groups. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.

  The group represented by-(MQ) is preferably a group having 1 to 30 carbon atoms, and more preferably a group having 5 to 20 carbon atoms. In particular, from the viewpoint of outgas suppression, a group having 6 or more carbon atoms is preferable.

As the group Y that is eliminated by the action of an acid, another preferred embodiment includes a structure represented by the following general formula (III).

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. However, not all of L ₃ , L ₄ and L ₅ are hydrogen atoms.
In addition, these cycloalkyl and aryl groups may contain a hetero atom.
Further, 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, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, A hexyl group and an octyl group are mentioned.

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 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 specifically includes a phenyl group, a tolyl group, a naphthyl group, and an anthryl 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 specifically includes a benzyl group and a phenethyl group.

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

L ₃ , L ₄ and L ₅ each preferably independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and more preferably L _{3 to} L ₅ are all an alkyl group or a cycloalkyl group. It is more preferable that L _{3 to} L ₅ are all alkyl groups.

L ₃ , L ₄ and L ₅ in the general formula (III) may have a substituent. Examples of this substituent include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, and acyloxy groups. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.

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

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

  In the polymer compound (A) of the present invention, the content of the repeating unit represented by the general formula (I) is in the range of 5 to 60 mol% with respect to all the repeating units in the polymer compound (A). Is preferable, the range of 10 to 45 mol% is more preferable, and the range of 15 to 40 mol% is particularly preferable.

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

In general 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 (m + 1) -valent aromatic ring group.
m represents an integer of 1 or more.

In the general formula (IV), examples of the substituent that the methyl group represented by R ₄ may have include specific examples and preferred ranges of the substituent that R ₁ in the general formula (I) may have. And the same substituents. R ₄ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

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

The (m + 1) -valent aromatic ring group represented by Ar ₂ may have a substituent other than the group represented by — (OH) _m , and the substituent is the above-described general formula. Specific examples of the substituent which R ₁ in (I) may have and substituents similar to the preferred ranges are exemplified.

  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.

In general formula (IV), when m is 1 and Ar ₂ is a phenylene group, the bonding position of —OH to the benzene ring of Ar ₂ is relative to the bonding position of the benzene ring to the polymer main chain. The para position, the meta position, and the ortho position may be used, but the para position or the meta position is preferable.

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

The repeating unit represented by the general formula (IV) is preferably a repeating unit represented by the following general formula (IV ′).

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

In the general formula _{(IV '), R 4,} Ar 2, and m have the same meanings as _R 4, _{Ar 2,} and m in the general formula (IV) above.

The repeating unit represented by the general 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 general formula (IV) are described below.

Among these, a preferable example of the repeating unit represented by the general formula (IV) is a repeating unit in which Ar ₂ is an unsubstituted phenylene group, and examples thereof include those described below.

  The content of the repeating unit represented by the general formula (IV) in the polymer compound (A) is 3 to 90 mol in the case of a positive resist composition with respect to all the repeating units in the polymer compound (A). % Is preferable, more preferably 5 to 90 mol%, and still more preferably 7 to 85 mol%.

  The polymer compound (A) may further have a repeating unit other than the repeating units described above. Examples thereof include a repeating unit which is stable against the action of an acid as described below.

More specifically, examples of the repeating unit stable to the action of an acid include a styrene derivative having a non-acid-decomposable substituent as exemplified by the general formula (V) and a general formula (VI). Such a repeating unit having a non-acid-decomposable aryl structure, cycloalkyl structure, or lactone structure in the side chain of the acrylic structure. By having this structure, adjustment of contrast, improvement in etching resistance, and the like can be expected.

In general 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 an acyl group. The alkyl group as Ra and Ra ₂ is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group as Ra and Ra ₂ may further have a substituent. As this substituent, halogen atoms, such as a fluorine atom and a chlorine atom, are mentioned, for example. Examples of the alkyl group for 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, particularly preferably a hydrogen atom or a methyl group.

B in the general formula (V) represents an acyl group, an alkyl group, an alkoxy group, an acyloxy group or an alkoxycarbonyl group, preferably an acyloxy group or an alkoxycarbonyl group, and more preferably an acyloxy group. Among acyloxy groups (represented by the general formula —O—CO—R _A , where R _A is an alkyl group), those having 1 to 6 carbon atoms in _RA are preferred, and those having 1 to 3 carbon atoms in _RA. Are more preferable, and those in which R _A has 1 carbon atom (that is, an acetoxy group) are particularly preferable.

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

  Each of the above groups may have a substituent, and preferred substituents include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group (methoxy group, Ethoxy group, propoxy group, butoxy group, etc.). As for the cyclic structure, examples of the substituent further include an alkyl group (preferably having 1 to 8 carbon atoms).

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

Specific examples of the repeating unit represented by the general formula (V) are shown below, but are not limited thereto.

In general formula (VI), R ₅ represents a non-acid-decomposable hydrocarbon group or 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 an acyl group. The alkyl group as Ra and Ra ₂ is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group as Ra and Ra ₂ may further have a substituent. As this substituent, halogen atoms, such as a fluorine atom and a chlorine atom, are mentioned, for example. Examples of the alkyl group for 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, particularly preferably a hydrogen atom or a methyl group.

R ₅ is preferably a hydrocarbon group having a cyclic structure or a lactone group. Specific examples in the case of having a cyclic structure include a monocyclic or polycyclic cycloalkyl group (preferably having 3 to 12 carbon atoms, more preferably 3 to 7 carbon atoms), a monocyclic or polycyclic cycloalkenyl group (carbon number). 3-12 are preferable), an aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms), a simple group. Examples thereof include a cyclic or polycyclic lactone group (preferably having 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms).

  Each of the above 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 or may not contain the repeating unit represented by the general formula (VI), but when it is contained, the content of the repeating unit represented by the general formula (VI) Is preferably 1 to 40 mol%, more preferably 2 to 20 mol%, based on all repeating units in the polymer compound (A).

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

  The polymer compound (A) used in the present invention may further have a repeating unit having a group capable of generating an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “photoacid generating group”) in the side chain. It is preferable because of excellent sensitivity. In this case, the compound (B) that generates an acid by actinic rays or radiation described later is not an independent compound but a single component in the polymer compound (A) according to the present invention. That is, as one embodiment of the present invention, the polymer compound (A) further includes a repeating unit having a group in the side chain that generates an acid upon irradiation with actinic rays or radiation, and the polymer compound (A) and the later-described compound. It is also preferable that the compound (B) is the same compound.

  Examples of the repeating unit having a photoacid-generating group include the repeating unit described in JP-A-9-325497 [0028] and the repeating units described in JP-A-2009-93137 [0038] to [0041]. Can be mentioned. In this case, it can be considered that the repeating unit having the photoacid-generating group corresponds to the compound (B) that generates an acid upon irradiation with an actinic ray or radiation of the present invention.

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

Examples of the repeating unit having a photoacid generating group in the side chain include a repeating unit represented by the following general 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 site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

Although the specific example of the repeating unit represented by General formula (5) below is shown, this invention is not limited to this.

  The polymer compound (A) of the present invention may be copolymerized with other polymerizable monomers capable of controlling film-forming properties and solvent solubility.

  Examples of these polymerizable monomers include hydrogenated hydroxystyrene, maleic anhydride, acrylic acid derivatives (acrylic acid, acrylic acid esters, etc.), methacrylic acid derivatives (methacrylic acid, methacrylic acid esters, etc.), N-substituted maleimides, Although acrylonitrile, methacrylonitrile, etc. can be mentioned, it is not limited to these.

In addition to the above, as a preferable repeating unit of the polymer compound, a unit having a cyclic structure in the main chain (such as a unit derived from a monomer having an indene structure), a unit having a naphthol structure, -C (CF ₃ ) ₂ Examples also include a repeating unit having an OH group.

  When the polymer compound (A) contains a repeating unit derived from these polymerizable monomers and the above-mentioned repeating unit, the content of these repeating units is from 1 to 1 with respect to all repeating units in the polymer compound (A). 30 mol% is preferable, More preferably, it is 1-10 mol%.

  In this invention, a high molecular compound (A) may be used independently and may be used in combination of 2 or more type.

  The mass average molecular weight of the polymer compound (A) used in the present invention is preferably 15000 or less, more preferably 1000 to 10,000, and particularly preferably 2000 to 8000.

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

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

  Here, the mass average molecular weight (Mw) and dispersity (Mw / Mn) of the polymer compound (A) are determined by a polystyrene-based GPC (gel permeation chromatography) method (solvent: THF).

  The polymer compound (A) can be synthesized by a known radical polymerization method or anionic polymerization method. For example, in the radical polymerization method, a vinyl monomer is dissolved in a suitable organic solvent, and a peroxide (benzoyl peroxide, etc.), a nitrile compound (azobisisobutyronitrile, etc.), or a redox compound (cumene hydroperoxide-first A polymer can be obtained by reacting at a room temperature or under a heating condition using an iron salt or the like) as an initiator. In the anionic polymerization method, a vinyl monomer can be dissolved in a suitable organic solvent, and a polymer can be obtained usually by reacting under a cooling condition using a metal compound (such as butyl lithium) as an initiator.

  It is also possible to synthesize by polymerizing a polymer using an unsaturated monomer corresponding to the precursor of each repeating unit and then modifying the synthesized polymer with a low molecular compound and converting it to a desired repeating unit. In any case, it is preferable to use living polymerization such as living anion polymerization because the obtained polymer compound has a uniform molecular weight distribution.

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

In the above specific example, tBu represents a t-butyl group.
The content of the group capable of decomposing with an acid includes the number of groups (B) capable of decomposing with an acid in the polymer compound (A) and the number of alkali-soluble groups not protected by a group capable of leaving with an acid (S). And is calculated by the formula B / (B + S). This content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

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

[2] Compound that generates acid upon irradiation with actinic ray or radiation The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound that generates an acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generator”). (B) "or" compound (B) ") is preferred, and it is more preferred to contain a compound that generates an acid other than carboxylic acid upon irradiation with actinic rays or radiation. As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro-resist etc. Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

Compounds represented by the following general formulas (ZI), (ZII), and (ZIII) as preferred compounds among the compounds capable of decomposing upon irradiation with actinic rays or radiation as the acid generator (B) Can be mentioned.

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

Z ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{− and the} like, preferably Is an organic anion containing a carbon atom. Preferable organic anions include organic anions represented by the following formulas AN1 to AN3.

In the formula _AN1~AN3, Rc 1 ~Rc ₃ each independently represents an organic group.

Examples of the organic group in Rc _{1 to} Rc ₃ include those having 1 to 30 carbon atoms, and preferably an alkyl group which may be substituted, an aryl group which may be substituted, or a plurality of these may be a single bond, _{-O -, - CO 2 -,} - S -, - SO 3 -, - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as. Further, it may form a ring structure with other bonded alkyl group or aryl group.
Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with another bonded alkyl group or aryl group.

The organic group of Rc _{1 to} Rc ₃ may be an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, 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 is increased and the sensitivity is improved. When Rc _{1 to} Rc ₃ have 5 or more carbon atoms, it is preferable that at least one carbon atom is substituted with a hydrogen atom, and it is more preferable that the number of hydrogen atoms is larger than that of fluorine atoms. By not having a perfluoroalkyl group having 5 or more carbon atoms, ecotoxicity is reduced.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.

Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.

Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

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

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of _R 201 _{to R 203} of a compound represented by (ZI) is, at least one bond with structure of _R 201 _{to R 203} of another compound represented by formula (ZI) It may be a compound.

  More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups _R 201 _{to R 203} in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group with the remaining being an alkyl group.

  Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, and an aryldialkylsulfonium compound.

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

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group. , Ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like.

Aryl group of R ₂₀₁ to R _203, an alkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group (Eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be included as a substituent. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, most preferably They are a C1-C4 alkyl group and a C1-C4 alkoxy group. The substituent may be substituted with any one of three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

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

Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group containing no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group not containing an aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

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, or a vinyl group, and more preferably a linear, branched, or cyclic 2- It is an oxoalkyl group or an alkoxycarbonylmethyl group, and most preferably a linear or branched 2-oxoalkyl group.

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

The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be linear, branched or cyclic, and is preferably a group having> C═O at the 2-position of the above alkyl group or cycloalkyl group Can be mentioned.

The alkoxy group in the alkoxycarbonylmethyl group as R _{201 to} R ₂₀₃ is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Two members out of R _{201 to} R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

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

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

R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.

R _6c and R _7c each independently represents a hydrogen atom or an alkyl group.

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

Any two or more of R _{1c to} R _7c may be bonded to form a ring structure. R _x and R _y may combine to form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond.

X ⁻ has the same meaning as Z ⁻ in formula (ZI).

  Specific examples of the compound (ZI-3) include the compounds exemplified in paragraphs 0047 and 0048 of JP-A-2004-233661, and paragraphs 0040 to 0046 of JP-A-2003-35948. it can.

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

In general formulas (ZII) and (ZIII), R _{204 to} R ₂₀₇ each independently have an aryl group that may have a substituent, an alkyl group that may have a substituent, or a substituent. Represents an optionally substituted cycloalkyl group.

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

Specific examples of the alkyl group and cycloalkyl group of R ₂₀₄ to R _207, as suitable are described as linear or branched alkyl group and cycloalkyl group as _R 201 _{to R 203} in the compound (ZI-2) It is the same as what I did.

Z ^- is, in the general formula (ZI) Z ^- synonymous.

Among the compounds that generate an acid upon irradiation with actinic rays or radiation as the acid generator (B), compounds represented by the following general formulas (ZIV), (ZV), and (ZVI) are further included. Can be mentioned.

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

R ₂₀₈ independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group in the general formulas (ZV) and (ZVI). In order to increase the strength of the generated acid, R ₂₀₈ is preferably substituted with a fluorine atom.

R ₂₀₉ and R ₂₁₀ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or an electron withdrawing group. R ₂₀₉ is preferably a substituted or unsubstituted aryl group. 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 alkenylene group, or a substituted or unsubstituted arylene group.

A compound having a plurality of structures represented by the general formula (ZVI) is also preferable in the present invention. For example, either R ₂₀₉ or R ₂₁₀ of the compound represented by the general formula (ZVI) has a structure bonded to either R ₂₀₉ or R ₂₁₀ of another compound represented by the general formula (ZVI). It may be a compound.

  Among the compounds that decompose as a result of irradiation with actinic rays or radiation to generate an acid other than a carboxylic acid, the acid generator (B) is more preferably a compound represented by general formulas (ZI) to (ZIII). Yes, more preferably a compound represented by (ZI), and most preferably a compound represented by (ZI-1) to (ZI-3).

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

  An acid generator (B) can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.

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

[3] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a basic compound. The basic compound is preferably a compound having a stronger basicity than phenol. The basic compound is preferably an organic basic compound, more preferably a nitrogen-containing basic compound. In one embodiment, an onium salt that is a weak acid relative to the acid generator may be used as the basic compound.

  Although the nitrogen-containing basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(7) can be used, Especially, (4) ammonium salt mentioned later is preferable.

(1) Compound represented by general formula (BS-1)

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

  Examples of the compound represented by the general formula (BS-1) (description of each group, specific examples of the compound represented by the general formula (BS-1), etc.) are described in JP-A-2013-015572. Reference can be made to the description of 0471-0481, the contents of which are incorporated herein.

(2) Compound having nitrogen-containing heterocyclic structure This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than nitrogen. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  Examples of compounds having a preferred nitrogen-containing heterocyclic structure include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and Aminoalkylmorpholine is mentioned. These may further have a substituent.

  Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.

  Particularly preferable basic compounds include, 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-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2- Amino-4-methylpyridine, 2-amino5-methylpyridine, 2-amino-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-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5 methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3 -Pyrazolin, N-aminomorpholine and N- (2-aminoethyl) morpholine.

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group is 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 is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is particularly preferable.

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

  The amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether, and adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. And then extracted with an organic solvent such as ethyl acetate and chloroform. In addition, the amine compound having a phenoxy group reacts by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal, and a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can also be obtained by adding an aqueous solution and then extracting with an organic solvent such as ethyl acetate and chloroform.

(4) Ammonium salt As the basic compound, an ammonium salt can be appropriately used, and a quaternary ammonium salt is preferable.

  The cation of the ammonium salt is preferably a tetraalkylammonium cation substituted with an alkyl group having 1 to 18 carbon atoms, such as a tetramethylammonium cation, a tetraethylammonium cation, a tetra (n-propyl) ammonium cation, or a tetra (i-propyl) ammonium. Cations, tetra (n-butyl) ammonium cation, tetra (n-heptyl) ammonium cation, tetra (n-octyl) ammonium cation, dimethylhexadecylammonium cation, benzyltrimethyl cation, etc. are more preferred, and tetra (n-butyl) ammonium Most preferred are cations.

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

  As the halide, chloride, bromide and iodide are particularly preferable.

  As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.

  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, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

  Examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As this substituent, a C1-C6 linear or branched alkyl group and a C3-C6 cycloalkyl group are preferable, for example. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferable. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The carboxylate may be an aliphatic carboxylate or an aromatic carboxylate, and examples thereof include acetate, lactate, bilbate, trifluoroacetate, adamantane carboxylate, hydroxyadamantane carboxylate, benzoate, naphthoate, salicylate, phthalate, phenolate, and the like. In particular, benzoate, naphthoate, phenolate and the like are preferable, and benzoate is most preferable.

  In this case, as the ammonium salt, tetra (n-butyl) ammonium benzoate, tetra (n-butyl) ammonium phenolate and the like are preferable.

  In the case of hydroxide, this ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). It is particularly preferred that

(5) A compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity ( PA)
The composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound that generates a compound that has been changed to acidity (hereinafter also referred to as compound (PA)).

  As a compound (PA) having a proton acceptor functional group and decomposing upon irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity Can be referred to the descriptions in paragraphs 0379 to 0425 of JP 2012-32762 A (corresponding to [0386] to [0435] of the corresponding US Patent Application Publication No. 2012/0003590), the contents of which are described in the present specification. Incorporated.

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

(6) Guanidine Compound The composition of the present invention may further contain a guanidine compound.

  As the guanidine compound, description in paragraphs 0374 to 0378 of JP 2012-32762 A (corresponding to [0382] to [0385] of the corresponding US Patent Application Publication No. 2012/0003590) can be referred to, and the contents thereof are described in this application. Incorporated in the description.

(7) Low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid The composition of the present invention comprises a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter referred to as “low molecular compound”). In this case, it is possible to contain “low molecular compound (D)” or “compound (D)”. The low molecular compound (D) preferably has basicity after the group capable of leaving by the action of an acid is eliminated.

  As the low molecular weight compound (D), description in paragraphs 0324 to 0337 of JP2012-133331A can be referred to, and the contents thereof are incorporated in the present specification.

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

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

  When the composition of the present invention contains an acid generator, the ratio of the acid generator and the compound (D) used in the composition is: acid generator / [compound (D) + the following basic compound] (mole Ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / [compound (D) + basic compound] (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

  Other examples that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, and compounds described in paragraph 0108 of JP-A No. 2007-298869. It is done.

  A photosensitive basic compound may be used as the basic compound. As the photosensitive basic compound, for example, JP-T-2003-524799 and J. Org. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) etc. can be used.

The onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently a sulfonium or iodonium cation.

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

  Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include the structures exemplified in paragraph [0198] of JP2012-242799A.

  Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include the structures exemplified in paragraph [0201] of JP2012-242799A.

  Preferable examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.

  The onium salt that is a weak acid relative to the acid generator is a compound (C) having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety being linked by a covalent bond ( (Hereinafter also referred to as “compound (CA)”).

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

In general formulas (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 the cation moiety and the anion moiety.

-X ^- it ^is, -COO _^-, -SO 3 _- represents an anion portion selected from _{^{-R 4 -, -SO 2 -,}} -N. R ₄ has 1 having a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, and a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. Represents a valent substituent.

R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In (C-3), two of R _{1 to} R ₃ may be combined 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, an alkylaminocarbonyl group, and a cycloalkylamino. A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

  Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.

  Preferable examples of the compound represented by the general formula (C-2) include the compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.

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

  The content of the onium salt that is a weak acid relative to the acid generator is preferably 0.5 to 10.0% by mass, and preferably 0.5 to 8.0% by mass based on the solid content of the composition. % Is more preferable, and 1.0 to 8.0% by mass is even more preferable.

  The molecular weight of the basic compound is usually 100-1500, preferably 150-1300, and more preferably 200-1000.

  These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

  When the composition according to the present invention contains a basic compound, the content is preferably 0.01 to 10.0% by mass based on the total solid content of the composition, It is more preferable that it is 8.0 mass%, and it is especially preferable that it is 0.2-5.0 mass%.

  The molar ratio of the basic compound to the photoacid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, More preferably, it is 0.1-3. The photoacid generator at the molar ratio is based on the total amount of the repeating unit represented by the general formula (5) of the resin and the photoacid generator that the resin may further contain. Is.

[4] Surfactant The composition of the present invention may further contain a surfactant. When contained, the surfactant is preferably a fluorine-based and / or silicon-based surfactant.

  Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd. and polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

  Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] et seq. Of US Patent Application Publication No. 2008 / 0248425A1.

Surfactants may be used alone or in combination of two or more.
The addition amount of the surfactant is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass with respect to the total solid content (total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %, Particularly preferably 0.0005 to 0.5 mass%.

[5] Hydrophobic resin The composition of the present invention may contain a hydrophobic resin.
The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film. However, unlike the surfactant, the hydrophobic resin does not necessarily have a hydrophilic group in the molecule and is polar / non-polar. It is not necessary to contribute to mixing the polar substance uniformly.

  Examples of the effect of adding the hydrophobic resin include control of static / dynamic contact angle of the actinic ray-sensitive or radiation-sensitive film surface with respect to water, suppression of outgassing, and the like.

The hydrophobic resin has at least one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have two or more types.

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

  When the hydrophobic resin contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.

  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 further a fluorine atom It may have a substituent other than.

  The cycloalkyl group having 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.

  Examples of the aryl group having a fluorine atom include those 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 having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.

Further, as described above, the hydrophobic resin preferably includes a CH ₃ partial structure in the side chain portion.

Here, the CH ₃ partial structure of the side chain portion in the hydrophobic resin (hereinafter also simply referred to as “side chain CH ₃ partial structure”) includes a CH ₃ partial structure of an ethyl group, a propyl group, or the like. Is.

On the other hand, methyl groups directly bonded to the main chain of the hydrophobic resin (for example, α-methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH ₃ partial structure in the present invention.

More specifically, when the hydrophobic resin includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). a _is, if R 11 _{to R 14} is CH ₃ "itself", the CH ₃ is not included in the CH ₃ partial structure contained in the side chain portion in the present invention.

Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R < ₁₁ > -R < ₁₄ > represents a side chain part each independently.

Examples of R _{11 to} R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.

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, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion. As such a repeating unit, the repeating unit represented by the following general formula (VII) and the following general unit It is more preferable to have at least one repeating unit (x) among the repeating units represented by the formula (VIII).

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

In the general formula (VII), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the organic group that is stable to acid is more preferably an organic group that does not have the “acid-decomposable group” described in the resin (A).

The alkyl group of _Xb1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and 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, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above 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 acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

Preferred specific examples of the repeating unit represented by the general formula (VII) are shown below. Note that the present invention is not limited to this.

The repeating unit represented by the general formula (VII) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
Hereinafter, the repeating unit represented by formula (VIII) will be described in detail.

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

The alkyl group of _Xb2 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.

X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable against acid, more specifically, R ₃ is preferably an organic group that does not have the “acid-decomposable group” described in the resin (A).

R ₃ includes an alkyl group having one or more CH ₃ partial structures.

The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.

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

Preferred specific examples of the repeating unit represented by formula (VIII) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (VIII) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion and, in particular, when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (VII) and the general formula ( The content of at least one repeating unit (x) among the repeating units represented by VIII) is preferably 90 mol% or more and 95 mol% or more with respect to all repeating units of the hydrophobic resin. It is more preferable. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin.

  The hydrophobic resin contains at least one repeating unit (x) among the repeating units represented by the general formula (VII) and the repeating unit represented by the general formula (VIII) as all the repeating units of the hydrophobic resin. On the other hand, the surface free energy of hydrophobic resin increases by containing 90 mol% or more. As a result, the hydrophobic resin tends to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film.

In addition, the hydrophobic resin includes the following groups (x) to (z) both when (i) a fluorine atom and / or a silicon atom are included, and (ii) when a side chain portion includes a CH ₃ partial structure. It may have at least one group selected from

(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) A group capable of decomposing by the action of an acid As the acid group (x), a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) ) Methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkyl) A carbonyl) methylene group, a tris (alkylsulfonyl) methylene group, and the like.

  Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

  The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.

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

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.

  As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.

  The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

  Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).

  The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin, and preferably 3 to 98. It is more preferable that it is mol%, and it is still more preferable that it is 5-95 mol%.

  Examples of the repeating unit having a group (z) that is decomposed by the action of an acid in the hydrophobic resin include the same repeating units having an acid-decomposable group as mentioned for the resin (A). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin, the content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 10%, based on all repeating units in the hydrophobic resin. It is 80 mol%, More preferably, it is 20-60 mol%.

  When hydrophobic resin has a fluorine atom, it is preferable that content of a fluorine atom is 5-80 mass% with respect to the mass mean molecular weight of hydrophobic resin, and it is more preferable that it is 10-80 mass%. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% in all the repeating units contained in hydrophobic resin, and it is more preferable that it is 30-100 mol%.

  When the hydrophobic resin has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the mass average molecular weight of the hydrophobic resin. Moreover, it is preferable that it is 10-100 mol% in the repeating unit containing a silicon atom in all the repeating units contained in hydrophobic resin, and it is more preferable that it is 20-100 mol%.

On the other hand, in the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, it is also preferred that the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom. The content of the repeating unit having an atom or silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, more preferably 1 mol% or less, based on all repeating units in the hydrophobic resin. More preferably, it is ideally 0 mol%, ie it does not contain fluorine and silicon atoms. Moreover, it is preferable that hydrophobic resin is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, it is preferable that the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in the total repeating units of the hydrophobic resin. 97 mol% or more is more preferable, 99 mol% or more is further preferable, and ideally 100 mol%.

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

  Moreover, the hydrophobic resin may be used alone or in combination.

  The content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass with respect to the total solid content in the composition of the present invention. 7 mass% is still more preferable.

  It is natural that the hydrophobic resin has few impurities such as metals, and the residual monomer or oligomer component is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, 0.05-1 mass% is still more preferable. Thereby, a composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

  As the hydrophobic resin, various commercially available products can be used, and can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.

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

[6] Compound having a monovalent iodine atom The composition of the present invention may contain a compound (AD) having a monovalent iodine atom. The sensitivity is improved when the composition contains the compound (AD). Examples of the compound (AD) include (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 “ Preferable examples include low molecular weight compound (AD2) ”. The resin (A) described above may also serve as the resin (AD1).

<(AD1) resin having monovalent iodine atom>
As resin (AD1) which has a monovalent iodine atom which a composition contains, resin which has the repeating unit (s) which has a monovalent iodine atom mentioned later is mentioned suitably, for example.

  5-100 mol% is preferable with respect to all the repeating units in resin (AD1), and content (it is the sum total when multiple types are contained) of the said repeating unit (s) in resin (AD1), 10-100 mol % Is more preferable, and 20-100 mol% is still more preferable.

  The resin (AD1) may have the same repeating units as those described as the repeating unit that the resin (A) may have, and the content of these repeating units in the resin (AD1) Same as (A).

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

<(AD2) Low molecular weight compound having a monovalent iodine atom>
Examples of the low molecular weight compound (AD2) having a monovalent iodine atom include a compound having a monovalent iodine atom and a molecular weight of less than 3000, preferably a compound having a molecular weight of less than 2000, and more preferably a compound having a molecular weight of less than 1500. More preferred are compounds having a molecular weight of less than 1000. Examples of the low molecular compound (AD2) having a monovalent iodine atom include a compound represented by the following general formula (2 ′).

In general 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 ₁ is an n-valent aromatic ring group.

  Examples of the monovalent aromatic ring group when n is 1 include an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a naphthyl group, an anthracenyl group, a biphenyl group, and a stilbenyl group, or, for example, Preferred examples include aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, triphenylamine.

  As a specific example of the n-valent aromatic ring group when n is an integer of 2 or more, (n-1) arbitrary hydrogen atoms are removed from the above-described specific example of the monovalent aromatic ring group. The group which can be mentioned can be mentioned suitably.

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

  Examples of the substituent that the n-valent aromatic ring group may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, and a halogen atom (iodine atom). ), An alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, and the like. The substituent preferably has 8 or less carbon atoms.

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

  RI is preferably an iodine atom.

n represents an integer of 1 or more. the upper limit value 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.

In the composition, the low molecular compound (AD2) can be used alone or in combination of two or more.
The content of the low molecular compound (AD2) in the composition is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, based on the total solid content in the composition. More preferred is mass%.

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

  More specifically, the repeating unit (s) is a repeating unit having a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation. That is, the repeating unit (s) has a partial structure having a monovalent iodine atom (hereinafter also referred to as “partial structure (s1)”), but this partial structure (s1) can be obtained by irradiation with actinic rays or radiation. , A partial structure that does not desorb from the repeating unit (s). Since the partial structure (s1) having a monovalent iodine atom is not eliminated even by irradiation with actinic rays or radiation, it is considered that high sensitivity can be obtained without reducing the light absorption effect.

  Here, the partial structure which decomposes | disassembles by irradiation of actinic light or a radiation is demonstrated.

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

Examples of the partial structure that decomposes upon irradiation with actinic rays or radiation include partial structures represented by the following general formulas (I) to (III). In addition, upon irradiation with actinic rays or radiation, the S atom-S atom bond is cleaved in the general formula (I), the O atom-N atom bond is cleaved in the general formula (II), and the O atom in the general formula (III). The -N atom bond is cleaved.

In general formulas (I) to (III),
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 alkenylene group, or a substituted or unsubstituted arylene group.

  In addition, the repeating unit (s) having a monovalent iodine atom may be a repeating unit having an acid-decomposable group. That is, in the repeating unit (s), it is not excluded that the partial structure (s1) having a monovalent iodine atom is a partial structure that is decomposed by the action of an acid to generate a polar group.

  In this case, the resin (AD1) only needs to have the repeating unit (s) and may not have the repeating unit (a) having the acid-decomposable group described above. In other words, in the resin (AD1) in this case, “a repeating unit having a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation” is decomposed by the action of an acid to polar groups. It also serves as a "repeat unit having a group that produces".

As such a repeating unit (s), for example, a repeating unit represented by the following general formula (1 ′) is preferably exemplified.

In general formula (1 ′),
R ₁₁ , R ₁₂ and R ₁₃ each independently represents 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, in which case R ₁₃ represents an alkylene group.

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

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 general formula (1 ′), the alkyl group represented by R _{11 to} R ₁₃ is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- which may have a substituent. Examples thereof include alkyl groups having 20 or less carbon atoms such as butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably alkyl groups having 3 or less carbon atoms. Can be mentioned.

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

  The cycloalkyl group may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.

  As a halogen atom, the halogen atom except an iodine atom is mentioned, for example.

When R ₁₃ is bonded to Ar ₁ to form a ring, examples of the alkylene group include alkylene groups having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. An alkylene group having 1 to 4 carbon atoms is preferable, and an alkylene group having 1 to 2 carbon atoms is more preferable.

The alkylene group in which X ₁ represents, for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, and an alkylene group having 1 to 8 carbon atoms such as octylene group, an alkylene group having 1 to 4 carbon atoms Preferably, an alkylene group having 1 to 2 carbon atoms is more preferable.

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-naphthylene group. 1,4-phenylene group is preferred.

Examples of the alkyl group represented by R in —NR— represented by X ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a hexyl group which may have a substituent. Group, a 2-ethylhexyl group, an octyl group, a dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, and an alkyl group having 8 or less carbon atoms are preferable.

Preferable examples of the divalent nitrogen-containing non-aromatic heterocyclic group represented by X ₁ include a group formed by removing two arbitrary hydrogen atoms from a heterocyclic ring such as pyrrole, pyrrolidine, piperidine and the like.

Among these, X ₁ is preferably a single bond, —COO—, —NR—, or a divalent linking group composed of a combination of these groups, and more preferably —COO—.

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

  As the divalent aromatic ring group when n is 1, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or, for example, thiophene, furan, pyrrole, Preferred examples include aromatic ring groups containing heterocycles such as benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like.

  Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.

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

  Examples of the substituent that the (n + 1) -valent aromatic ring group may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, and a halogen atom ( An iodine group), an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, and the like. The substituent preferably has 8 or less carbon atoms.

The aromatic ring group represented by Ar ₁ is preferably a phenylene group, a naphthylene group, or a group formed by removing (n-1) arbitrary hydrogen atoms from these groups.

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

  RI is preferably an iodine atom.

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

  n is preferably an integer of 2 or more, and more preferably an integer of 3 or more, because of higher sensitivity and higher resolution.

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

  In the resin (AD1), only one type of repeating unit (s) may be used, or two or more types may be used.

  The content of the repeating unit (s) in the resin (AD1) (the total when there are a plurality of types) is preferably from 0.1 to 80 mol%, based on the total repeating units in the resin (AD1). 1-50 mol% is more preferable and 1-30 mol% is still more preferable.

[7] Resist solvent The solvent that can be used in preparing the composition is not particularly limited as long as it dissolves each component. For example, alkylene glycol monoalkyl ether carboxylate (propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane)), alkylene glycol monoalkyl ether (propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol), etc.), alkyl lactate ester (ethyl lactate, methyl lactate, etc.), cyclic lactone (Gamma-butyrolactone, etc., preferably 4 to 10 carbon atoms), chain or cyclic ketone (2-heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms), alkylene carbonate (ethylene carbonate) , Propylene carbonate), alkyl acetate such as carboxylic acid alkyl (butyl acetate is preferred), and the like alkoxy alkyl acetates (ethyl ethoxypropionate). Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

  Of the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.

  These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and 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 the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.

  The amount of the solvent used in the total amount of the composition of the present invention can be appropriately adjusted according to the desired film thickness and the like, but generally the total solid content concentration of the composition is preferably 0.5 to 5% by mass, preferably Is adjusted to 0.8 to 3% by mass, more preferably 0.8 to 2% by mass, and still more preferably 0.8 to 1.5% by mass.

[8] Other additives In addition to the components described above, the composition of the present invention includes a carboxylic acid onium salt, a dissolution inhibiting compound having a molecular weight of 3000 or less, a dye described in Proceeding of SPIE, 2724, 355 (1996), and the like. , Plasticizers, photosensitizers, light absorbers, antioxidants, and the like can be appropriately contained.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. <Synthesis Example 1: Synthesis of polymer compound (P1)>
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 this solution, 10.40 g of 2-cyclohexylethyl vinyl ether and 1.45 g of 2% by mass camphorsulfonic acid (PGMEA solution) were added as a vinyl ether compound, and the mixture was stirred at room temperature for 2 hours. 1.05 g of 10% by mass triethylamine (PGMEA solution) was added and stirred for a while, and then the reaction solution was transferred to a separatory funnel containing 165 mL of ethyl acetate. This organic layer was washed three times with 200 mL of distilled water, and then ethyl acetate was removed with an evaporator. The obtained reaction solution was dropped into 2 L of hexane, and the supernatant was removed. The obtained product was dissolved in 95 g of PGMEA, and the low boiling point solvent was removed under reduced pressure conditions to obtain 132.3 g of a PGMEA solution (28.3 mass%) of the polymer compound (P1).

With respect to the polymeric compound ^(P1), using a 1 H-NMR and ¹³ C-NMR, was determined molar ratios of the respective repeating units. Moreover, the polystyrene conversion mass average molecular weight (Mw) and dispersity (Mw / Mn) were calculated | required using GPC (solvent: THF). The results are shown in Table 1 below. In the table, the “composition ratio” column describes the molar ratio of each repeating unit (corresponding in order from the left).

<Synthesis Example 2: Synthesis of polymer compound (P2)>
25.5 g of p-hydroxystyrene (53.1% by mass 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 (sum) Koganei Pharmaceutical Co., Ltd.) was dissolved in 31.4 g of propylene glycol monomethyl ether (PGME). 10.8 g of PGME was put in the reaction vessel and dropped into the system at 85 ° C. in a nitrogen gas atmosphere over 2 hours. 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. The diluted solution was dropped into 1000 g of heptane / ethyl acetate (mass ratio) = 8/2 to precipitate the polymer and filtered. Thereafter, the solid was subjected to vacuum drying to obtain 36.32 g of a polymer compound (P2).

  In Table 1, other polymer compounds (P3) to (P-10) were synthesized using the same method as that for the polymer compound (P1) or (P2).

Polymer-X1 was synthesized by a known radical polymerization method using p-acetoxystyrene and t-butyl methacrylate.

[Compositions 1-11]
Each component shown in the following Table 2 was dissolved in the solvent shown in the same table. This was filtered using a polyethylene filter having a pore size of 0.1 μm.

Details of each component other than the polymer compound (A) abbreviated in Table 2 are shown below. <Acid generator (B)>

<Basic compound> TBAH: Tetrabutylammonium hydroxide DBN: 1,5-diazabicyclo [4.3.0] non-5-ene TDA: tri-n-decylamine <Surfactant> W-1: Megafac F176 (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: Examples 1-9, Comparative Example 1 ~ 3>
A resist pattern was formed by the following operations using the compositions 1 to 11 shown in Table 2. Details of the resist pattern forming conditions are shown in Table 3.

[Resist coating and pre-baking (PB)]
The prepared positive resist solution was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. Next, heat drying was performed at 120 ° C. for 90 seconds using a hot plate.

〔exposure〕
Using a electron beam irradiation apparatus (JBX6000 manufactured by JEOL Co., Ltd .; acceleration voltage 50 keV) for the resist film, a line pattern having a line width of 20 nm in increments of 2.5 nm (length direction 0.5 mm, number of drawing 40 lines) Were exposed at different doses.

[Post exposure bake (PEB)]
Immediately after exposure, it was heated on a hot plate at 110 ° C. for 90 seconds.

〔developing〕
1. Shower development Using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.), the alkaline developer (23 ° C.) shown in Table 3 was rotated at a flow rate of 200 mL / min while rotating the wafer at 50 rpm (rpm). Development was performed by spraying for the time indicated in Table 3.

  Thereafter, rinsing treatment was performed by spraying for 30 seconds at a flow rate of 200 mL / min using pure water as a rinsing liquid (23 ° C.) while rotating the wafer at 50 rpm.

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

2. Paddle development Using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.), while rotating the wafer at 50 rpm (rpm), the alkaline developer (23 ° C.) shown in Table 3 at a flow rate of 200 mL / min. The developer was deposited on the wafer by spraying for 5 seconds. Subsequently, the rotation of the wafer was stopped, and the development was performed by leaving the wafer to stand for the time shown in Table 3.

  Thereafter, rinsing treatment was performed by spraying for 30 seconds at a flow rate of 200 mL / min using pure water as a rinsing liquid (23 ° C.) while rotating the wafer at 50 rpm.

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

  The resist pattern was evaluated for the following items. Details of the results are shown in Table 4.

[Line edge roughness (LER)]
Measure the distance from the reference line where there should be an edge, using a scanning electron microscope (S-9380II, manufactured by Hitachi, Ltd.) for any 30 points in the 1 μm length direction of a line pattern with a line width of 20 nm. The deviation was calculated and 3σ was calculated. The smaller this value, the better the line edge roughness.

[CDU]
A line-and-space pattern with a line width of 20 nm was measured with a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) at 50 locations at intervals of 2 mm, and the standard deviation at 50 locations was obtained and calculated as 3σ. did. The smaller this value, the better the line width uniformity and the better the performance.

[EL]
The exposure amount that forms a line and space with a line width of 20 nm was taken as the optimal exposure amount, and the value obtained by dividing the exposure amount width that reproduces the line width of 20 nm ± 10% by the optimal exposure amount value was expressed as a percentage (%). The larger this value, the smaller the line width variation (the greater the tolerance) with respect to the exposure amount change, and the better the performance.

From the results shown in Table 4, it can be seen that the resist pattern forming method according to the present invention can simultaneously satisfy a good CDU, a small line edge roughness (LER), and a wide exposure margin (EL). <EUV exposure: Examples 10 to 18 and Comparative Examples 4 to 6>
A resist pattern was formed and evaluated in the same manner as in the EB exposure except that exposure was performed using EUV light (wavelength 13 nm) using a 1: 1 line and space mask pattern having a line width of 24 nm. Table 5 shows the pattern formation conditions, and Table 6 shows the pattern evaluation results.

  From the results shown in Table 6, the resist pattern forming method according to the present invention has good CDU, small line edge roughness (LER), and wide exposure margin (EL) even when EUV light (wavelength 13 nm) is used. It can be understood that

Claims (14)

A step of applying an actinic ray-sensitive or radiation-sensitive resin composition on a substrate to form an actinic ray-sensitive or radiation-sensitive film;
-A step of exposing the actinic ray-sensitive or radiation-sensitive film; and-a pattern forming method comprising a step of developing the actinic-ray-sensitive or radiation-sensitive film after exposure using an alkali developer;
The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a polymer compound containing a repeating unit represented by the following general formula (I),
The concentration of the alkali component of the alkali developing solution is Ri 1.25 mass% to 2.2% by mass, the film thickness of the actinic ray-sensitive or radiation-sensitive film is 60nm or less, the pattern forming method.
In general formula (I), R ₀₁ , R ₀₂ and R ₀₃ each independently represents 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, in which case 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.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 5. The pattern formation method of Claim 1 whose film thickness of the said actinic-ray-sensitive or radiation-sensitive film is 15 nm or more and 50 nm or less. The pattern formation method of Claim 1 whose film thickness of the said actinic-ray-sensitive or radiation-sensitive film is 15 nm or more and 40 nm or less. The pattern formation method according to claim 1, wherein the actinic ray-sensitive or radiation-sensitive film has a thickness of 15 nm to 30 nm. The pattern forming method according to claim 1, wherein the alkaline developer is an aqueous solution containing tetramethylammonium hydroxide. The pattern forming method according to claim 5 , wherein the alkaline developer contains alcohols. The pattern forming method according to claim 5 , wherein the alkaline developer contains a surfactant. The pattern forming method according to claim 5 , wherein the exposure in the exposure step is performed by an electron beam or EUV light. The pattern formation method according to claim 5 , wherein in general formula (I), at least one Y is a group represented by the following general formula (II).
In the formula, 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 amino group, an ammonium group, a mercapto 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 formation method according to claim 9 , wherein at least one of L ₁ and L _{2 in} the general formula (II) is an atom adjacent to the carbon atom in the formula is a tertiary or quaternary carbon atom. The pattern formation method according to claim 5 , wherein in general formula (I), at least one Y is a group represented by the following general formula (III).
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. However, not all of L ₃ , L ₄ and L ₅ are 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 5 , wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains (B) a compound that generates an acid upon irradiation with actinic rays or radiation. A method for manufacturing a photomask, comprising the pattern forming method according to claim 12 . A method for producing a mold for nanoimprinting, comprising the pattern forming method according to claim 12 .