TW201510662A - Pattern forming method and surface treatment agent used in the same, and method for producing electronic device and electronic device - Google Patents

Abstract

The invention provides a pattern forming method, which sequentially includes: (1) a step for forming an actinic ray-sensitive or a radioactive ray-sensitive film by an actinic ray-sensitive or a radioactive ray-sensitive resin composition, wherein the actinic ray-sensitive or the radioactive ray-sensitive resin composition contains a resin which decomposes to generate a polar group because of a reaction of an acid; (2) a step for exposing the actinic ray-sensitive or the radioactive ray-sensitive film; (4A) a step for reacting a surface treatment agent with the actinic ray-sensitive or the radioactive ray-sensitive film, wherein the surface treatment agent contains a compound interacting with the polar group contained by the resin after exposure; and (5A) a step for using a developing liquid including an organic solvent to develop the actinic ray-sensitive or the radioactive ray-sensitive film.

Description

Pattern forming method and surface treating agent therefor, and manufacturing method and electronic component of electronic component

The present invention relates to a semiconductor manufacturing step applicable to an integrated circuit (IC), a circuit substrate for manufacturing a liquid crystal, a thermal head, and the like, and other photolithography lithography. A pattern forming method of a step, a surface treating agent therefor, a method of manufacturing an electronic component, and an electronic component. In particular, the present invention relates to a pattern forming method suitable for exposure of an ArF exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, a surface treatment agent therefor, and a method of manufacturing an electronic component and an electronic component .

After the resist for the KrF excimer laser (248 nm), a pattern forming method using chemical amplification is used in order to compensate for the decrease in sensitivity caused by light absorption. For example, in the positive chemical amplification method, first, the photoacid generator contained in the exposed portion is decomposed by light irradiation to generate an acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process, etc., by the catalyst of the generated acid The action causes the alkali-insoluble group contained in the photosensitive composition to change to an alkali-soluble group. Thereafter, development is carried out, for example, using an alkaline solution. Thereby, the exposed portion is removed to obtain a desired pattern.

Among the methods described above, various alkaline developing solutions have been proposed as alkaline developing solutions. For example, an aqueous alkaline developing solution of a 2.38 mass% aqueous solution of Tetramethyl Ammonium Hydroxide (TMAH) is usually used as the alkaline developing solution.

In order to refine the semiconductor element, the short wavelength of the exposure light source and the high numerical aperture (high numerical aperture) of the projection lens have been developed. Currently, an ArF excimer laser having a wavelength of 193 nm is being developed as a light source. Exposure machine. As a technique for further improving the resolving power, a method of filling a liquid having a high refractive index between the projection lens and the sample (hereinafter also referred to as "liquid immersion liquid") (that is, a liquid immersion method) is proposed. In addition, Extreme Ultraviolet (EUV) lithography that uses a shorter wavelength (13.5 nm) of ultraviolet light for exposure is also advocated.

However, the actual situation is that it is extremely difficult to find an appropriate combination of a resist composition, a developing solution, an eluent, and the like required for forming a pattern having excellent overall performance, and further improvement is required.

In recent years, a pattern forming method using a developing solution containing an organic solvent has been developed (for example, refer to Patent Document 1 and Patent Document 2).

Prior art literature

Patent literature

Patent Document 1: Japanese Patent No. 4554665

Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-310314

However, in the above-mentioned literature, there is no description of a pattern forming method capable of forming a pattern having a flat top of a pattern or a pattern having excellent pattern remnancy during double development, and there is room for further improvement.

An object of the present invention is to provide a pattern forming method capable of forming a pattern having excellent flatness at the top of a pattern or a pattern at the time of double development, a surface treatment agent therefor, and a method of manufacturing an electronic component. And electronic components.

The invention is as follows.

[1] A pattern forming method comprising: (1) a step of forming a photosensitive ray-sensitive or radiation-sensitive film by a sensitizing ray-sensitive or radiation-sensitive resin composition, the sensitizing ray property or The radiation sensitive linear resin composition contains a resin which decomposes due to the action of an acid and generates a polar group; (2) a step of exposing the photosensitive ray-sensitive or radiation-sensitive film; (4A) containing and exposing the resin a step of treating a surface of the compound having a polar group to interact with the sensitizing ray-sensitive or radiation-sensitive film; and (5A) using the developing solution containing an organic solvent for the sensitizing ray or feeling The step of developing the radiation linear film.

[2] A pattern forming method comprising: (1) a step of forming a sensitized ray-sensitive or radiation-sensitive film by a sensitizing ray-sensitive or radiation-sensitive resin composition, or The radiation sensitive resin composition contains a resin which decomposes due to the action of an acid and generates a polar group; (2) a step of exposing the photosensitive ray-sensitive or radiation-sensitive film; (3) using an alkaline developer solution a step of developing a photosensitive ray-sensitive or radiation-sensitive film to obtain a first development pattern; and (4B) applying a surface treatment agent containing a compound that interacts with a polar group of the resin after exposure to the first a step of developing a pattern; and (5B) further developing the first developing pattern using a developing solution containing an organic solvent to obtain a second developing pattern.

[3] The pattern forming method according to [2], wherein between the step (2) and the step (3), (6) heating the sensitized ray-sensitive or radiation-sensitive film And the step (3) between the step (3) and the step (4B), comprising (7) the first development pattern at a temperature higher than a temperature of 30 ° C or higher than the temperature of the heating in the step (6) The step of heating.

[4] The pattern forming method according to [2] or [3], wherein between the step (4B) and the step (5B), comprising (8) heating the first developing pattern step Step.

[5] The pattern forming method according to any one of [1] to [4] wherein the surface treatment agent contains a basic compound as the compound which interacts with a polar group.

[6] The pattern forming method according to [5], wherein the surface treatment agent contains, as the basic compound, a resin having a repeating unit having a basic functional group.

[7] The pattern forming method according to [5], wherein the basic compound contains a compound selected from the group consisting of a tertiary amino group, a quaternary ammonium group, and a substituent having a nitrogen atom as a ring member. At least one of the group consisting of heteroaryl groups.

[8] The pattern forming method according to any one of [1] to [7] wherein the compound which interacts with a polar group is soluble in the step (5A) or the step (5B) In a developer of an organic solvent.

[9] The pattern forming method according to any one of [1] to [8] wherein the surface treatment agent contains a solvent, and the step (4A) or the step (4B) comprises contacting the surface treatment agent The step of sensitizing the surface of the radioactive or radiation sensitive film.

[10] The pattern forming method according to [9], wherein the surface treatment agent contains The solvent used is a solvent having a film dissolution rate at 23 ° C of 0.1 nm/s or less when the unexposed coating film of the sensitizing ray-sensitive or radiation sensitive film is used.

[11] The pattern forming method according to any one of [1] to [8] wherein the step (4A) or the step (4B) comprises contacting the vapor of the surface treatment agent with the sensitizing ray property. Or the step of sensing the surface of the radioactive film.

[12] The pattern forming method according to any one of [1] to [11] wherein the exposure is liquid immersion exposure.

[13] A method of producing an electronic component, comprising the pattern forming method according to any one of [1] to [12].

[14] An electronic component manufactured by the method of manufacturing an electronic component according to [13].

[15] A surface treatment agent for use in the pattern forming method according to any one of [1] to [12].

[16] A surface treating agent comprising a resin, and a solvent containing a monohydric alcohol, the resin containing a repeating unit having a basic functional group.

According to the present invention, it is possible to provide a pattern forming method capable of forming a pattern having excellent flatness at the top of a pattern or a pattern at the time of double development, a surface treating agent therefor, a method for producing an electronic device, and an electronic device.

1‧‧‧Substrate

2‧‧‧Photosizing ray-sensitive or radiation-sensitive linear film

3‧‧‧First development pattern

4‧‧‧second development pattern

11‧‧‧Exposure Department

12‧‧‧Unexposed Department

13‧‧‧Intermediate Exposure Department

13a‧‧‧ sidewall of the intermediate exposure

14‧‧‧ Space Department

21‧‧‧Surface treatment agent

Fig. 1 is a schematic cross-sectional view showing a photosensitive ray-sensitive or radiation-sensitive film after the step (1).

Fig. 2 is a schematic cross-sectional view showing a photosensitive ray-sensitive or radiation-sensitive film after the step (2).

Fig. 3 is a schematic cross-sectional view showing the first development pattern after the step (3).

Fig. 4 is a schematic cross-sectional view showing the second development pattern after the step (5B).

5(a), 5(b), 5(c), and 5(d) are schematic cross-sectional views for explaining the fluctuation of the line width of the first developing pattern in the step (4B).

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

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

In addition, "actinic ray" or "radiation" in the present specification means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, and an extreme ultraviolet ray. (EUV light), X-ray, electron beam, and the like. Further, in the present invention, light means actinic rays or radiation. The "exposure" in this specification refers to exposure by a mercury lamp, a far-ultraviolet light represented by a quasi-molecular laser, X-rays, EUV light, etc., using a beam of electron beams or ion beams, unless otherwise specified. The depiction made is also included in the exposure.

<pattern forming method>

The first pattern forming method of the present invention includes, in order, the steps of: (1) forming a photosensitive ray-sensitive or radiation-sensitive film by a sensitizing ray-sensitive or radiation-sensitive resin composition, or The radiation sensitive linear resin composition contains a resin which decomposes due to the action of an acid to generate a polar group (hereinafter also referred to as "resin (A)"); (2) exposes the sensitized ray-sensitive or radiation-sensitive film (4A) a step of allowing a surface treatment agent containing a compound that interacts with a polar group possessed by the exposed resin to act on the sensitized ray-sensitive or radiation-sensitive film; and (5A) using organic The developing solution of the solvent develops the photosensitive ray-sensitive or radiation-sensitive film.

Thereby, it is possible to provide a pattern forming method capable of forming a pattern having excellent flatness on the top of the pattern, a surface treating agent therefor, a method of manufacturing the electronic component, and an electronic component. Although the reason is not clear, for example, it is estimated as follows.

The first pattern forming method of the present invention comprises, between step (2) and step (5A), (4A) a surface containing a compound which interacts with a polar group The treatment agent acts on the step of sensitizing the radioactive or radiation sensitive film.

Therefore, in the exposed portion of the sensitizing ray-sensitive or radiation-sensitive film, it is considered that the polar group-based contact on the surface of the sensitizing ray-sensitive or radiation-sensitive film interacts with the polar group to interact with each other. The insolubilization of organic solvents is further developed.

As a result, it is considered that the surface of the exposed portion of the exposed portion of the radiation sensitive film or the radiation sensitive film is suppressed at the time of development, and the flatness of the top portion of the formed pattern is improved.

The second pattern forming method of the present invention includes, in order, the steps of: (1) forming a photosensitive ray-sensitive or radiation-sensitive film by a sensitizing ray-sensitive or radiation-sensitive resin composition, or The radiation sensitive resin composition contains a resin which decomposes due to the action of an acid and generates a polar group; (2) a step of exposing the photosensitive ray-sensitive or radiation-sensitive film; (3) using an alkaline developer solution a step of developing a photosensitive ray-sensitive or radiation-sensitive film to obtain a first development pattern; and (4B) applying a surface treatment agent containing a compound that interacts with a polar group of the resin after exposure to the first a step of developing a pattern; and (5B) developing the first developing pattern using a developing solution containing an organic solvent to obtain a second developing pattern.

Thereby, it is possible to provide a pattern forming method which is excellent in flatness at the top of the pattern and which is excellent in pattern remnancy at the time of double development, a surface treatment agent therefor, a method for producing an electronic element, and an electronic element. Although the reason is not clear, for example, it is estimated as follows.

The second pattern forming method of the present invention, between the step (3) and the step (5B), includes (4B) a surface treatment agent containing a compound which interacts with a polar group possessed by the exposed resin. The step of the first developing pattern.

First, a method of forming a pattern by the pattern forming method will be described.

1 to 4 are schematic cross-sectional views showing the photosensitive ray-sensitive or radiation-sensitive film after the step (1), and a schematic cross-sectional view and a description of the sensitizing ray-sensitive or radiation-sensitive film after the step (2). A schematic cross-sectional view of the first development pattern after the step (3) and a schematic cross-sectional view of the second development pattern after the step (5B).

In the second pattern forming method of the present invention, first, as shown in FIG. 1, a sensitizing ray-sensitive or radiation sensitive film 2 is formed on the substrate 1. Thereafter, through the step (2), as shown in FIG. 2, the exposure portion 11, the unexposed portion 12, and the intermediate exposure portion 13 are formed in the photosensitive ray-sensitive or radiation-sensitive film. Here, for example, when the threshold value T ₁ and the threshold value T ₂ in the exposure amount are defined so as to become T ₁ > T ₂ , the exposure unit 11 is a region in which the exposure amount is T ₁ or more, and the unexposed portion 12 In the region where the exposure amount is less than T ₂ , the intermediate exposure portion 13 is a region in which the exposure amount is T ₂ or more and less than T ₁ .

Next, the exposure unit 11 is dissolved in an alkaline developing solution, and the sensitizing ray-sensitive or radiation-sensitive film is developed, and as shown in FIG. 3, an intermediate portion including the unexposed portion 12 and the unexposed portion 12 is formed. The first developing pattern 3 of the exposure portion 13.

Then, after the surface treatment agent is applied to the first development pattern 3, the unexposed portion 12 is dissolved using a developing solution containing an organic solvent, and the first development pattern 3 is further developed, thereby forming an inclusion as shown in FIG. Second of the intermediate exposure portion 13 Development pattern 4.

In the second pattern forming method of the present invention, as described above, between the step (3) and the step (5B), a surface treatment agent containing a compound which interacts with a polar group possessed by the exposed resin is included. The step of acting on the first developing pattern 3.

Thereby, the surface treatment agent enters into the space portion 14 of the first development pattern 3 sandwiched by the intermediate exposure portion 13, and the polar group existing in the side wall 13a of the intermediate exposure portion 13 contacts the compound that interacts with the polar group. Create interactions. As a result, even if the developer containing the organic solvent in the step (5B) enters the space portion 14, it is suppressed that the intermediate exposure portion 13 is dissolved in the developer containing the organic solvent, and the double development (that is, the alkali is used) The pattern remnancy at the time of development of the development of the developer and the development of the developer containing the organic solvent is improved.

Further, since the top portion of the intermediate exposure portion 13 is also in contact with the surface treatment agent, the dissolution of the developer containing the organic solvent is also suppressed, and as a result, the flatness of the top of the pattern is considered to be improved.

Further, in the step (4B), the surface treatment agent of the present invention penetrates into the intermediate exposure portion 13 or adheres to the surface of the intermediate exposure portion 13 to form an interaction. Therefore, the reflection is by infiltration. Attached. The volume variation caused by various physical/chemical interactions and the like, and the line width of the pattern after the step (4B) can be changed as compared with the line width of the pattern before the step (4B).

More specifically, for example, the first development pattern 3 including the unexposed portion 12 and the intermediate exposure portion 13 that sandwiches the unexposed portion 12 (refer to FIG. 5(a); further, FIG. 5(a) In the same manner as in FIG. 3, the intermediate exposure portion 13 is expanded by penetration of the surface treatment agent (see FIG. 5(b)), or the surface treatment agent 21 is attached to the intermediate exposure portion 13, or the intermediate exposure portion 13 is treated with the surface. The interaction of the agents results in volume contraction (see Figure 5(c)).

Hereinafter, each step included in the pattern forming method of the present invention will be described in detail.

(1) a step of forming a photosensitive ray-sensitive or radiation-sensitive film composition by a photosensitive ray-sensitive or radiation-sensitive resin composition containing an action of an acid Polar based resin

The first pattern forming method and the second pattern forming method of the present invention include the step (1).

The photosensitive ray-sensitive or radiation-sensitive film in the step (1) is a film formed of the photosensitive ray-sensitive or radiation-sensitive resin composition in the step (1), and more specifically, preferably by sensitizing A film formed by coating a radiation-sensitive or radiation-sensitive resin composition on a substrate. In the pattern forming method of the present invention, the step of forming a film formed of a photosensitive ray-sensitive or radiation-sensitive resin composition on a substrate can be carried out by a generally known method.

In the present invention, the substrate on which the film is formed is not particularly limited, and an inorganic substrate such as ruthenium, SiN, SiO ₂ or SiN, a coated inorganic substrate such as spin-on glass (SOG), or the like can be used. The manufacturing steps, the manufacturing steps of the circuit substrate such as a liquid crystal or a thermal head, and the substrate generally used in the lithography step of other photosensitive etching processes. Further, an organic anti-reflection film may be formed between the film and the substrate as needed.

It is also preferred to include a pre-heating step (Prebake (PB)) after film formation and before the exposure step.

In addition, after the exposure step and before the development step, a post-exposure heating step (Post Exposure Bake (PEB)) is also preferred.

Preferably, the PB and the PEB are carried out at a heating temperature of 70 ° C to 130 ° C, more preferably at 80 ° C to 120 ° C.

The heating time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and even more preferably from 30 seconds to 90 seconds.

Heating can be done by usual exposure. The apparatus provided in the developing machine may be carried out, or may be performed using a heating plate or the like.

The reaction of the exposed portion is promoted by baking, and the sensitivity or pattern outline is improved.

(2) Step of exposing the sensitizing ray-sensitive or radiation-sensitive linear film

The first pattern forming method and the second pattern forming method of the present invention include the step (2).

The wavelength of the light source used in the exposure method of the present invention is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., and a far ultraviolet light having a wavelength of preferably 250 nm or less. Light, more preferably a far-ultraviolet light having a wavelength of 220 nm or less, particularly a far-ultraviolet light having a wavelength of 1 nm to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ standard Molecular laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., preferably KrF excimer laser, ArF excimer laser, EUV or electron beam, more preferably ArF excimer laser.

Further, a liquid immersion exposure method can be applied in the exposure step of the present invention. The liquid immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a deformation illumination method.

When immersion exposure is performed, the step of washing the surface of the film with a water-based chemical solution may be performed after (1) forming a film on the substrate and before performing the exposure, and/or (2) via liquid immersion. After the step of exposing the film to the film, the step of washing the surface of the film with the aqueous solution is performed before the step of heating the film.

The liquid immersion liquid is preferably transparent to the exposure wavelength, and in order to minimize the deformation of the optical image projected on the film, the temperature coefficient of the refractive index is as small as possible, especially when the exposure light source is an ArF excimer. In the case of the emission (wavelength: 193 nm), in addition to the above viewpoints, water is preferably used from the viewpoints of easiness of obtaining, ease of handling, and the like.

When water is used, it is also possible to add an additive (liquid) which reduces the surface tension of water and increases the interfacial activity in a minute ratio. Preferably, the additive does not dissolve the resist layer on the wafer and may ignore the effects on the optical coating on the lower surface of the lens element.

As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples thereof include methanol, ethanol, and isopropyl alcohol. By adding an alcohol having a refractive index substantially equal to that of water, it is possible to obtain an advantage that the refractive index change of the entire liquid can be minimized even if the concentration of the alcohol component in the water evaporates to cause a change in the concentration.

On the other hand, when mixed with a substance that is opaque to 193 nm or refraction When the impurity is not the same as the water, the optical image projected on the resist is deformed. Therefore, as the water to be used, distilled water is preferred. Further, pure water filtered by an ion exchange filter or the like can also be used.

The electric resistance of the water used as the liquid immersion liquid is preferably 18.3 M?cm or more, and the TOC (organic matter concentration) is desirably 20 ppb or less, and desirably, the degassing treatment is performed.

In addition, the lithographic performance can be improved by increasing the refractive index of the liquid immersion liquid. From this point of view, an additive such as a refractive index-increasing additive may be added to water or heavy water (D ₂ O) may be used instead of water.

The recoil contact angle of the sensitized ray-sensitive or radiation-sensitive film formed by using the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention at a temperature of 23±3° C. and a humidity of 45±5% is 70° or more It is suitable for exposure through a liquid immersion medium, and the receding contact angle of the sensitized ray-sensitive or radiation sensitive film is preferably 75° or more, more preferably 75° to 85°.

If the receding contact angle is too small, it is not suitable for exposure by a liquid immersion medium, and the effect of reducing water mark (watermark) defects cannot be sufficiently exhibited. In order to achieve a preferable receding contact angle, it is preferred to contain a hydrophobic resin (HR) to be described later in the sensitizing ray-sensitive or radiation-sensitive composition. Alternatively, a coating layer (so-called "top coat") formed of a hydrophobic resin composition may be formed on the sensitized ray-sensitive or radiation-sensitive film to thereby increase the receding contact angle.

The top coat layer which can be applied is not particularly limited, and those well known in the art can be suitably used. In addition, an application such as Japanese Patent Laid-Open Publication No. 2013-61647 can also be considered. In particular, the top coat layer containing a basic compound (quenching agent) containing not only a resin but also a resin as described in OC-5 to OC-11 of Table 3 of the examples provides an auxiliary function for pattern shape adjustment and the like.

In the immersion exposure step, the liquid immersion liquid is required to follow the action of scanning the exposure head on the wafer at a high speed and forming an exposure pattern, so that the liquid immersion liquid in a dynamic state is sensitive to sensitization or The contact angle of the radiation sensitive film becomes important, and the resist is required to have no residual liquid droplets and follow the high-speed scanning performance of the exposure head.

(3) A step of developing a photosensitive ray-sensitive or radiation-sensitive film using an alkaline developing solution to obtain a first developing pattern

Further, the second pattern forming method of the present invention comprises the step (3). In the second pattern forming method, the spatial frequency of the optical image can be expected by the combination of the step (3) and the step (5B) as described in FIG. 1-FIG. 11 and the like of US Pat. 1/2 pattern.

The alkaline developing solution in the step (3) contains water as a main component. In addition, the main component means that the content of water exceeds 50% by mass based on the total amount of the developer.

As the developer, from the viewpoint of further improving the solubility of the pattern, it is preferred to use an alkaline aqueous solution containing a base.

The type of the basic aqueous solution is not particularly limited, and examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and tetraamylammonium hydroxide. , tetrahexylammonium hydroxide, tetraoctyl ammonium hydroxide, ethyl trimethyl ammonium hydroxide, butyl trimethyl ammonium hydroxide, methyl tripentyl ammonium hydroxide, a tetraalkylammonium hydroxide such as dibutylammonium hydroxide or a tetraalkylammonium hydroxide such as trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide or triethylbenzylammonium hydroxide; An alkaline aqueous solution of a base, a primary amine, a secondary amine, a tertiary amine, an alcoholamine, a cyclic amine or the like. Among them, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide is preferred.

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

An appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution for use. Specific examples and amounts of the surfactant are the same as those of the organic developer described later.

The alkali concentration of the alkaline aqueous solution is usually from 0.1% by mass to 20% by mass.

The pH of the alkaline aqueous solution is usually from 10.0 to 15.0.

Usually, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide is used. Further, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution for use.

After the step (3), the rinsing may be carried out, and as the eluent in the rinsing treatment after the alkali development, pure water may be used, and an appropriate amount of the surfactant may be added and used.

(4A) a step of applying a surface treatment agent containing a compound which interacts with a polar group of the resin after exposure to a sensitizing ray-sensitive or radiation-sensitive film, and (4B) a resin containing the exposed resin Polar group Step of applying a surface treating agent of the interacting compound to the first developing pattern

The first pattern forming method of the present invention includes the step (4A).

The surface treatment agent in the step (4A) preferably contains a solvent, and the step (4A) is preferably a step of contacting the surface treatment agent with the surface of the sensitizing ray-sensitive or radiation-sensitive film.

The polar group of the resin after the exposure is not particularly limited as long as it is a polar group which the resin has after exposure, but it is preferably decomposed and produced by the action of an acid after exposure. Polar base.

As a contact method of the surface treatment agent, for example, a method of immersing a sensitizing ray-sensitive or radiation-sensitive film or a first development pattern in a tank filled with a surface treatment agent for a fixed time (dipping method); by utilizing surface tension a method of depositing a surface treatment agent onto a surface of a sensitizing ray-sensitive or radiation-sensitive film or a first developing pattern and stationary for a fixed period of time (covering method); spraying the surface treating agent to sensitized ray or radiation Film or method for first developing pattern surface (spray method); scanning surface treatment agent ejection nozzle at a fixed speed while continuously ejecting onto a photosensitive ray-sensitive or radiation-sensitive film or first development pattern rotating at a fixed speed Method for surface treating agent (dynamic dispensing method); method for applying a surface treating agent to a sensitizing ray-sensitive or radiation-sensitive film or a first developing pattern to form a surface treating agent film on the pattern; and sensitizing the ray The method of exposing the radiation treatment film or the first development pattern to the vapor of the surface treatment agent, etc., preferably applying the surface treatment agent to the sensitization A linear or radiation-sensitive film or a first developing a pattern, a surface treatment film is formed on the pattern.

The details of the surface treatment agent used in the step (4A) will be described later.

The second pattern forming method of the present invention comprises the step (4B).

Specific examples and preferred examples of the contact treatment method of the surface treatment agent and the surface treatment agent used in the step (4B) are the same as those in the step (4A).

The surface treatment agent may be a gas (preferably ammonia gas) or a solution as long as it contains the compound (A) to be described later, but is preferably a solution. In other words, the surface treatment agent preferably contains a solvent. In this case, preferably, in the first pattern forming method and the second pattern forming method of the present invention, the step (4A) and the step (4B) respectively include contacting the surface treating agent with the sensitized ray The step of sexually or sensitizing the surface of a radioactive film. When the surface treatment agent is a solution, the total mass of the compound (A) is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 0.1% by mass based on the total amount of the surface treatment agent. 5 mass% or less, more preferably 1 mass% to 5 mass%, still more preferably 1 mass% to 3% mass%. Further, in the present invention, the compound (A) may be used alone or in combination of two or more compounds having different chemical structures.

Further, as described above, the surface treatment agent may be a gas, and in this case, preferably in the first pattern forming method and the second pattern forming method of the present invention, the step (4A) and the step ( 4B) respectively includes a step of bringing the vapor of the surface treatment agent into contact with the surface of the photosensitive ray-sensitive or radiation-sensitive film.

When the surface treatment agent is a solution, the amount of use thereof is not particularly limited as long as it can sufficiently interact with the polar group of the resin after exposure. It is preferred to use an amount that covers at least the entire surface of the substrate. The specific amount of use depends on the concentration of the surface treatment agent, the viscosity, the thickness of the sensitizing ray or the radiation sensitive film, and the size of the substrate. For example, when the substrate is a wafer having a diameter of 300 mm, the amount of application is used. It is suitable to be adjusted within the range of 0.1 mL to 100 mL.

(5A) a step of developing a sensitizing ray-sensitive or radiation-sensitive film using a developing solution containing an organic solvent (hereinafter also referred to as "organic developing solution"), and (5B) further using a developing solution containing an organic solvent Developing the first developing pattern to obtain a second developing pattern

The first pattern forming method of the present invention includes the step (5A).

Further, the second pattern forming method of the present invention includes the step (5B). Thereby a negative pattern is formed.

As the organic developing solution, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent or an ether solvent, or a hydrocarbon solvent can be used.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, and 1- Hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, purple Rotorone, diacetone alcohol, acetamethanol, acetophenone, methylnaphthyl ketone, isophorone, propyl carbonate, and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and propylene glycol monomethyl. Ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxyl Propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate , butyl lactate, propyl lactate and the like.

Examples of the alcohol-based solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, and n-octanol. An alcohol such as n-nonanol or a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, or A glycol ether solvent such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol.

Examples of the ether solvent include dioxane, tetrahydrofuran, and the like, in addition to the glycol ether solvent.

As the amide-based solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine can be used. , 1,3-dimethyl-2-imidazolidinone, and the like.

Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon solvent such as toluene or xylene, and an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

In particular, the organic developing solution preferably contains a developing solution containing at least one organic solvent selected from the group consisting of a ketone solvent and an ester solvent, and particularly preferably contains butyl acetate or a ketone as an ester solvent. A solvent solution of methyl amyl ketone (2-heptanone).

The solvent may be mixed in a plurality of kinds, and may be used in combination with a solvent or water other than the above. However, in order to sufficiently obtain the effects of the present invention, it is preferred that the entire developing solution The water content is less than 10% by mass, and more preferably it is substantially free of moisture.

In other words, the amount of the organic solvent to be used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less based on the total amount of the developer.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 °C. By setting the vapor pressure of the organic developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved, resulting in uniform dimensional uniformity in the wafer surface. .

In the organic developer, an appropriate amount of a surfactant may be added as needed.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based surfactant and/or a lanthanoid surfactant can be used. Examples of the fluorine-based surfactants and/or the lanthanum-based surfactants include, for example, JP-A-62-36663, JP-A-61-226746, and JP-A-61-226745. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -54432, Japanese Patent Laid-Open No. Hei 9-5988, U.S. Patent No. 5,405, 720, U.S. Patent No. 5,360, 692, U.S. Patent No. 5,529, 881, U.S. Patent No. 5,296,330, U.S. Patent No. 5,436,098, The surfactant described in the specification of U.S. Patent No. 5,576,143, U.S. Patent No. 5,294,511, and U.S. Patent No. 5,824,451 is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, but is more preferably In order to use a fluorine-based surfactant or a quinone-based surfactant.

The amount of the surfactant to be used is usually 0.001% by mass to 5% by mass, preferably 0.005% by mass to 2% by mass, and more preferably 0.01% by mass to 0.5% by mass based on the total amount of the developer.

Further, the organic developer may contain a basic compound as needed. Examples of the basic compound include a nitrogen-containing basic compound, and examples thereof include a nitrogen-containing compound described in [0021] to [0063] of JP-A-2013-11833. When the organic developing solution contains a basic compound, it is expected to enhance the contrast at the time of development, suppress film thinning, and the like.

As the developing method, the same method as the developing method in the above step (3) can be mentioned.

When the various developing methods include a step of ejecting the developing solution from the developing nozzle of the developing device toward the photosensitive ray or the radiation sensitive film or the first developing pattern, as an example, the discharge pressure of the discharged developing solution (discharged) The flow rate per unit area of the developer is preferably 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, still more preferably 1 mL/sec/mm ² or less. The flow rate does not particularly have a lower limit, but it is preferably 0.2 mL/sec/mm ² or more in consideration of the treatment amount. The details of this are described in Japanese Patent Laid-Open No. 2010-232550, especially paragraphs 0022 to 0029.

Further, after the step of developing using a developing solution containing an organic solvent, the step of stopping the development while replacing the solvent with another solvent may be employed.

(6) Steps for heating a sensitizing ray-sensitive or radiation-sensitive linear film And (7) a step of heating the first developing pattern at a temperature higher than a temperature of the heating in the step (6) by 30 ° C or higher

Preferably, the second pattern forming method of the present invention comprises, between the step (2) and the step (3), comprising (6) a step of heating the photosensitive ray-sensitive or radiation-sensitive film, Between the step (3) and the step (4B), comprising (7) heating the first development pattern at a temperature higher than a temperature of 30 ° C higher than the temperature of the heating in the step (6). step. By the heating, an acid generated in a compound which generates an acid by irradiation with actinic rays or radiation remaining in the intermediate exposure portion in the first developing pattern, and decomposition by an action of an acid Further, the resin which generates the polar group reacts again, and further accelerates the decomposition of the resin in the intermediate exposure portion. As a result, it is considered that the pattern remaining property at the time of double development is further improved.

The heating temperature in the step (6) is preferably from 70 ° C to 130 ° C, more preferably from 80 ° C to 120 ° C.

The heating time in the step (6) is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and even more preferably from 30 seconds to 90 seconds.

The heating in step (6) can be by ordinary exposure. The apparatus provided in the developing machine may be carried out, or may be performed using a heating plate or the like.

The heating temperature in the step (7) is preferably from 100 ° C to 160 ° C, more preferably from 110 ° C to 150 ° C.

The heating time in the step (7) is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and still more preferably from 30 seconds to 90 seconds.

The heating in step (7) can be by ordinary exposure. The apparatus provided in the developing machine may be carried out, or may be performed using a heating plate or the like.

(8) Step of heating the first developing pattern

The second pattern forming method of the present invention preferably includes the step of heating (8) the first developing pattern between the step (4B) and the step (5B).

The heating temperature in the step (8) is preferably from 70 ° C to 130 ° C, more preferably from 80 ° C to 120 ° C.

The heating time in the step (8) is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and even more preferably from 30 seconds to 90 seconds.

Heating can be done by usual exposure. The apparatus provided in the developing machine may be carried out, or may be performed using a heating plate or the like.

(9) rinsing step

The first pattern forming method and the second pattern forming method of the present invention preferably include a rinsing step of washing with an eluent after the step (4A) and the step (4B). The eluent is not particularly limited as long as the resist pattern is dissolved, and a solution containing a general organic solvent can be used. As the eluent, it is preferred to use at least one organic solvent containing a group selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. Eluent.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent are the same as those exemplified in the developer containing the organic solvent.

In one aspect of the present invention, after the development step, an eluent containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent is used. In the step of washing, it is more preferred to carry out the step of washing with an eluent containing an alcohol solvent or an ester solvent, and it is particularly preferable to carry out a step of washing with a rinse containing a monohydric alcohol, and it is preferable to carry out the use of carbon. The step of washing the eluent of the monohydric alcohol having 5 or more.

Here, examples of the monohydric alcohol used in the elution step include linear, branched, and cyclic monohydric alcohols. Specifically, 1-hexanol, 2-hexanol, and 4-methyl- can be used. 2-pentanol (methyl isobutylmethanol), 1-pentanol, 3-methyl-1-butanol, and the like.

The components may be mixed in a plurality of types, or may be used in combination with an organic solvent other than the above.

The water content in the eluent is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. Good development characteristics can be obtained by setting the water content to 10% by mass or less.

The vapor pressure of the eluent used after the step of developing using a developing solution containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 at 20 °C. kPa or more and 3 kPa or less. By setting the vapor pressure of the eluent to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling due to the penetration of the eluent is suppressed, and the dimensions in the wafer surface are uniform. Sex is better.

An appropriate amount of surfactant can also be added to the eluent for use.

In the step of eluting, using the eluent containing an organic solvent, the use package The developed developer containing the organic solvent is subjected to a cleaning process. The method of the cleaning treatment is not particularly limited, and for example, a method of continuously ejecting the eluent onto a substrate rotating at a fixed speed (a spin coating method) and a method of immersing the substrate in a tank filled with the eluent for a fixed time can be applied. (dipping method), a method of spraying the eluent onto the surface of the substrate (spraying method), etc., wherein the cleaning treatment is preferably performed by a spin coating method, and after the cleaning, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm. The eluent is removed from the substrate. In addition, it is also preferred to include a heating step (Post Bake) after the rinsing step. The developer and the eluent remaining between the patterns and the inside of the pattern are removed by baking. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, preferably 70 ° C to 95 ° C, for usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The organic developing solution, the alkaline developing solution, and/or the eluent used in the present invention preferably have less impurities such as various fine particles or metal elements. In order to obtain such a chemical liquid having a small amount of impurities, it is preferable to produce the chemical liquid in a clean room, and to filter by various filters such as a Teflon filter, a polyolefin filter, or an ion exchange filter. And reduce impurities. The metal element preferably has a metal element concentration of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn of 10 ppm or less, more preferably 5 ppm or less.

In addition, the storage container of the developer or the eluent is not particularly limited, and a container such as a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin used in the use of an electronic material can be suitably used, in order to reduce dissolution from the container. It is also preferable that the container is selected from the inner wall of the container and has a small amount of components which are eluted into the chemical liquid. As such a capacity The container may be a container of a perfluoro resin (for example, a FluoroPure Perfluoroalkoxy (PFA) composite barrel manufactured by Entegris (liquid inner surface; PFA resin lining). , Steel cans (Jet inner surface; zinc phosphate film) manufactured by JFE.

(10) Step of forming a protective film by a composition for forming a protective film

The second pattern forming method of the present invention may include (10) a sensitized ray-sensitive or radiation-sensitive film (hereinafter, also referred to as first photosensitive) between the step (1) and the step (2). The step of forming a protective film by a composition for forming a protective film on a ray-sensitive or radiation-sensitive film, in which case it is preferable to include (10') the first sensitizing ray or the radiation radiance a step of forming a second sensitized ray-sensitive or radiation-sensitive film by a second sensitizing ray-sensitive or radiation-sensitive resin composition different from the sensitizing ray-sensitive or radiation-sensitive resin composition on the film, The second sensitizing ray-sensitive or radiation-sensitive resin composition contains a resin which decomposes due to the action of an acid and generates a polar group.

The protective film-forming composition (particularly the second sensitized ray-sensitive or radiation-sensitive resin composition which is a preferred embodiment of the protective film-forming composition) will be described in detail later.

As a method of forming a protective film by a composition for forming a protective film on the first sensitized ray-sensitive or radiation-sensitive film, the sensitizing ray or sensitizing radiation described in the above step (1) can be employed. The method of forming a film is the same.

(11) Step of removing the upper portion of the first developing pattern

The second pattern forming method of the present invention may be in the step (4B) and the step Between steps (5B), the step of removing the upper portion of the first developing pattern is included (11), and in this case, it is preferable to include (11') a step of etching the first developing pattern.

The etching in the step (11') may be a dry etching or a wet etching, but is preferably a dry etching.

Examples of the dry etching method include, for example, Japanese Patent Laid-Open No. 59-126506, Japanese Patent Laid-Open No. Sho 59-46628, Japanese Patent Laid-Open No. Sho 58-9108, Japanese Patent Laid-Open No. Sho 58-2809, and Japan. The method described in Japanese Laid-Open Patent Publication No. Sho 57-148706, and the like.

As the etching gas to be used for the dry etching, a mixed gas containing one or more gases (main etching gas) selected from a fluorine-based gas, nitrogen gas, ammonia gas, and hydrogen gas and oxygen gas is preferably used.

The main etching gas can be processed with an anisotropic effect on the organic film by a combination with oxygen.

Further, in the mixed gas of the present invention, the mixing ratio of the main etching gas and oxygen (main etching gas/oxygen) is preferably 1/1 to 10/1 in terms of a flow ratio. By setting it as the said range, the formation of the deposition product (deposited film) which generate|occur|produces on the side wall at the time of the etching, and the balance of the etching become favorable, can suppress the growth of a deposition film toward a side wall, and can suppress a resist. The generation of the most damaged layer at the surface. As a result thereof, the upper portion of the first developing pattern can be easily removed. The mixing ratio is preferably 7/1 to 3/1, more preferably 6/1 to 4/1, in terms of a flow ratio.

The mixed gas in the present invention preferably contains, in addition to the gas, a gas selected from the group consisting of helium (He) and helium, from the viewpoint of the stability of the partial pressure control of the etching plasma. At least one third gas in the group of inert gases such as (Ne), argon (Ar), helium (Kr), and xenon (Xe) is used as the other gas. In this case, the mixing ratio of the third gas and the main etching gas (the third gas/main etching gas) is preferably 1/1 to 1/3 in terms of the flow rate ratio. However, when the partial pressure controllability of the etching gas can be maintained, it is not necessary to mix the third gas.

The internal pressure of the cavity at the time of etching is preferably from 0.5 Pa to 4.0 Pa, more preferably from 1.0 Pa to 4.0 Pa. When the internal pressure of the cavity is in the above range, the rectangularity of the pattern becomes good, and deposition of the deposited film formed by etching toward the side wall can be suppressed. The internal pressure of the chamber can be adjusted, for example, by suitably controlling the flow rate of the etching gas and the degree of pressure reduction of the chamber.

The flow rate of the mixed gas at the time of etching is preferably 1,500 sccm or less, and more preferably 1200 sccm or less. Here, sscm refers to a flow rate (mL/min) in a standard state (1 atm (atmospheric pressure: 1013 hPa), 0 ° C).

Further, the applied high frequency may be selected from 400 kHz, 60 MHz, 13.56 MHz, 2.45 GHz, etc., and may be performed by a radio frequency (RF) power of preferably 50 W to 2000 W, more preferably 100 W to 1000 W. deal with.

The dry etching may terminate the dry etching according to the etching processing time calculated in advance, or the end point detector may be used to detect the end point of the dry etching process.

Additionally, the etch may include an over etch process. The overetching treatment is preferably performed after setting the overetching ratio. Further, the overetching ratio is preferably calculated based on the time of the etching process that is initially performed. The overetching ratio can be arbitrarily set, but the etching resistance of the upper portion of the first developing pattern and the rectangularity of the etched pattern are maintained. From the viewpoint, it is preferably 30% or less, more preferably 5% to 25%, and particularly preferably 10% to 15% of the etching treatment time in the etching.

The pattern obtained by the method of the present invention is typically used as a mask in an etching step such as semiconductor fabrication. In addition, it can also be used as a core material (core) of a spacer process as disclosed in Japanese Patent Laid-Open No. Hei 3-270227 and Japanese Patent Laid-Open No. Hei No. 2013-164509. Further, it can be suitably used for guiding pattern formation in Directed Self-Assembly (DSA) (for example, refer to "ACS Nano" Vol. 4 No. 8 4815 - 4823) ). In addition, it can be applied to various purposes.

The present invention also relates to a method of manufacturing an electronic component including the pattern forming method of the present invention, and an electronic component manufactured by the method.

The electronic component of the present invention is an electronic component that is suitably mounted on an electric and electronic device (home appliance, office automation (OA), media-related device, optical device, communication device, etc.).

<surface treatment agent>

Hereinafter, the surface treatment agent (hereinafter also referred to as "the surface treatment agent of the present invention") used in the present invention will be described in detail.

The surface treatment agent contains a compound that interacts with a polar group (hereinafter also referred to as "compound (A)").

The compound (A) is not particularly limited as long as it interacts with a polar group, but it is preferred that at least one of ionic bonding, hydrogen bonding, chemical bonding, and dipole interaction can be formed for a polar group. Compound. As described above, by resin (A) The interaction with the surface treatment agent changes the solubility of the resin (A), and the flatness of the top of the pattern and the pattern residual property at the time of double development become excellent. Further, the term "ion bonding" means electrostatic interaction between a cation and an anion, and also includes formation of a salt or the like.

In view of the fact that the effect of the present invention is excellent, at least one selected from the group consisting of a phosphonium salt compound, a nitrogen-containing compound, and a phosphorus-based compound is exemplified as the compound (A).

The compound (A) may be in the form of a low molecular compound or in the form of a polymer compound, but is preferably in the form of a polymer compound.

Hereinafter, the form of the low molecular compound among various compounds will be described in detail first.

[low molecular compound]

(鎓 salt compound)

The onium salt compound means a compound having a phosphonium salt structure. Further, the sulfonium salt structure refers to a salt structure formed by a coordination bond between an organic component and a Lewis base. The onium salt compound forms an interaction with the polar group mainly by ionic bonding. For example, when the polar group is a carboxyl group, the cation in the onium salt compound forms an electrostatic interaction (formation of ionic bonding) with the carboxyl group-derived carboxyl anion (COO ⁻ ).

The type of the onium salt structure is not particularly limited, and examples thereof include an ammonium salt, a phosphonium salt, an oxonium salt, a phosphonium salt, a selenium salt, a carbonium salt, a diazonium salt, a phosphonium salt, etc. having a cationic structure shown below. structure.

In addition, as a cation in the sulfonium salt structure, a hetero atom in a heteroaromatic ring is also included. A person with a positive charge on the child. Examples of such an onium salt include a pyridinium salt, an imidazolium salt, and the like.

Further, in the present specification, the pyridinium salt or the imidazolium salt is also included as one form of the ammonium salt.

The sulfonium salt compound may be a polyvalent sulfonium salt compound having two or more cesium ion atoms in one molecule from the viewpoint of further excellent effects of the present invention. The polyvalent sulfonium salt compound is preferably a compound in which two or more cations are linked by a covalent bond.

Examples of the polyvalent onium salt compound include a diazonium salt, a phosphonium salt, and a phosphonium salt. Ammonium salt, barium salt. Among them, from the viewpoint of more excellent effects of the present invention, a diazonium salt, a phosphonium salt, a phosphonium salt, and an ammonium salt are preferable, and in terms of stability, an ammonium salt is more preferable.

In addition, an anion (negative ion) contained in the onium salt compound (anthracene salt structure) may be any one as long as it is an anion, and may be a monovalent ion or a multivalent one. ion.

For example, examples of the monovalent anion include a sulfonate anion, a formate anion, a carboxylate anion, a sulfinate anion, a boron anion, a halide ion, a phenol anion, an alkoxy anion, and a hydroxide ion. Further, examples of the divalent anion include an oxalate ion, a phthalate ion, a maleate ion, a fumarate ion, a tartrate ion, a malate ion, and a lactate ion. Sulfate ion, diglycolate ion, 2,5-furandicarboxylate ion, and the like.

More specifically, as the monovalent anion, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , F(HF) _n ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , C ₉ H ₁₉ COO ^- , (CH ₃ ) ₂ PO ₄ ^- , (C ₂ H ₅ ) ₂ PO ₄ ^- , C ₂ H ₅ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , CH ₃ (OC ₂ H ₄ ) ₂ OSO ₃ ^- , C ₆ H ₄ (CH ₃ )SO ₃ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , CH ₃ CH(OH)COO ^- , B(C ₆ F ₃ ) ₄ ^- , FSO ₃ ^- , C ₆ H ₅ O ^- , (CF ₃ ) ₂ CHO ^- , (CF ₃ ) ₃ CHO ^- , C ₆ H ₃ ( CH ₃ ) ₂ O ^- , C ₂ H ₅ OC ₆ H ₄ COO ^- and the like.

Among them, a sulfonate anion, a carboxylate anion, a bis(alkylsulfonyl)guanamine anion, a tris(alkylsulfonyl)methide anion, BF ₄ ^- , PF ₆ ^- , SbF ₆ can be preferably exemplified. ^- and the like, more preferably an organic anion containing a carbon atom.

Specific examples of the cations contained in the onium salt structure are exemplified below.

[Chemical 4]

Specific examples of the anion contained in the onium salt structure are exemplified below.

Specific examples of the onium salt structure are exemplified below.

[Chemistry 7]

[化8]

[Chemistry 9]

[化10]

[11]

[化12]

As a suitable form of the onium salt compound, the onium salt compound represented by the formula (1-1) and the onium salt compound represented by the formula (1-2) are preferable from the viewpoint of the effect of the present invention being more excellent. At least one of the group consisting of.

In addition, the onium salt compound represented by the formula (1-1) may be used alone or in combination of two or more. In addition, the onium salt compound represented by the formula (1-2) may be used alone or in combination of two or more. Further, the onium salt compound represented by the formula (1-1) and the onium salt compound represented by the formula (1-2) may be used in combination.

[Chemistry 13]

In the formula (1-1), M represents a nitrogen atom, a phosphorus atom, a sulfur atom, or an iodine atom. Among them, from the viewpoint that the effect of the present invention is more excellent, a nitrogen atom is preferred.

Each of R independently represents a hydrogen atom, an aliphatic hydrocarbon group which may contain a hetero atom, an aromatic hydrocarbon group which may contain a hetero atom, or a combination of two or more of these.

The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic chain. Further, the number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but from the viewpoint of further excellent effects of the present invention, it is preferably from 1 to 15, more preferably from 1 to 5.

Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkene group, an alkyne group, or a combination of two or more of these.

The aliphatic hydrocarbon group may also contain a hetero atom. That is, it may be a hydrocarbon group containing a hetero atom. The type of the hetero atom to be contained is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a ruthenium atom. For example, -Y ₁ H, -Y ₁ -, -N(R _a )-, -C(=Y ₂ )-, -CON(R _b )-, -C(=Y ₃ )Y ₄ -, -SO _T- , -SO ₂ N(R _c )-, a halogen atom, or a form in which two or more of these are combined.

Y ₁ to Y ₄ are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a germanium atom. Among them, from the viewpoint of easier handling, an oxygen atom or a sulfur atom is preferred.

The R _a , R _b , and R _c are each independently selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

t represents an integer from 1 to 3.

The number of carbon atoms contained in the aromatic hydrocarbon group is not particularly limited, but from the viewpoint of further excellent effects of the present invention, it is preferably 6 to 20, more preferably 6 to 10.

Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

The aromatic hydrocarbon group may also contain a hetero atom. The form containing a hetero atom is as described above. Further, when the aromatic hydrocarbon group contains a hetero atom, it may constitute an aromatic heterocyclic group.

As a suitable form of R, from the viewpoint of further excellent effects of the present invention, an alkyl group which may contain a hetero atom, an olefin group which may contain a hetero atom, a cycloalkyl group which may contain a hetero atom, and a hetero atom may be contained. Aryl.

Further, a plurality of Rs may be bonded to each other to form a ring. The type of the ring to be formed is not particularly limited, and examples thereof include a 5-membered ring structure and a 6-membered ring structure.

Further, the ring to be formed may have an aromatic character, and for example, the cation of the onium salt compound represented by the formula (1-1) may be a pyridinium ring represented by the following formula (10). Further, a part of the formed ring may contain a hetero atom. For example, the cation of the onium salt compound represented by the formula (1-1) may be an imidazolium ring represented by the following formula (11).

Further, the definition of R in the formula (10) and the formula (11) is as described above.

In the formula (10) and the formula (11), Rv each independently represents a hydrogen atom or an alkyl group. A plurality of Rvs may be bonded to each other to form a ring.

X ^- represents a monovalent anion. The definition of monovalent anions is as described above.

In the formula (1-1), n represents an integer of 2 to 4. Further, when M is a nitrogen atom or a phosphorus atom, n represents 4, when M is a sulfur atom, n represents 3, and when M is an iodine atom, n represents 2.

In the formula (1-2) M, R and X ^- as defined above. Furthermore, in the formula (1-2), two X ^{− are} contained.

L represents a divalent linking group. The divalent linking group may, for example, be a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having a carbon number of 1 to 8. For example, an alkylene group such as a methylene group, an ethyl group or a propyl group). a substituted or unsubstituted divalent aromatic hydrocarbon group (preferably having a carbon number of 6 to 12, such as a phenyl group), -O-, -S-, -SO ₂ -, -N(R) -(R:alkyl), -CO-, -NH-, -COO-, -CONH-, or a combination of two or more of these (for example, an alkoxy group, an alkoxycarbonyl group, Alkyl carbonyloxy group, etc.).

Among them, from the viewpoint of more excellent effects of the present invention, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group is preferred.

In the formula (1-2), m each independently represents an integer of 1 to 3. Further, when M is a nitrogen atom or a phosphorus atom, m represents 3, when M is a sulfur atom, m represents 2, and when M is an iodine atom, m represents 1.

(nitrogen-containing compounds)

The nitrogen-containing compound means a compound containing a nitrogen atom. Further, in the present specification, the onium salt compound is not contained in the nitrogen-containing compound. The nitrogen-containing compound forms an interaction between the nitrogen atom in the compound and the polar group. For example, when the polar group is a carboxyl group, it interacts with a nitrogen atom in the nitrogen-containing compound to form a salt.

The nitrogen-containing compound may, for example, be a compound represented by the following formula (6).

In the above formula (6), R ⁴ and R ⁵ each independently represent a hydrogen atom, a hydroxyl group, a decyl group, an alkoxy group, an alkoxycarbonyl group, a chain hydrocarbon group having 1 to 30 carbon atoms, and a carbon number of An alicyclic hydrocarbon group of 3 to 30, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or a combination of two or more of these groups. R ⁶ is a hydrogen atom, a hydroxyl group, a decyl group, an alkoxy group, an alkoxycarbonyl group, an n-valent chain hydrocarbon group having 1 to 30 carbon atoms, an n-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms, An n-valent aromatic hydrocarbon group having 6 to 14 carbon atoms or an n-valent group in which two or more kinds of these groups are combined. n is an integer of 1 or more. However, when n is 2 or more, a plurality of R ⁴ and R ⁵ may be the same or different. Further, any two of R ⁴ to R ⁶ may be bonded and form a ring structure together with the nitrogen atom to which they are bonded.

Examples of the chain hydrocarbon group having 1 to 30 carbon atoms represented by the above R ⁴ and R ⁵ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and a 2-methyl group. Base, 1-methylpropyl, tert-butyl, and the like.

Examples of the aliphatic cyclic hydrocarbon group having 3 to 30 carbon atoms represented by the above R ⁴ and R ⁶ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by the above R ⁴ and R ⁶ include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the group in which two or more of these groups are represented by the above R ⁴ and R ⁵ include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. 6 to 12 aralkyl groups, etc.

The n-valent chain hydrocarbon group having 1 to 30 carbon atoms represented by the above R ⁶ is, for example, a chain having a carbon number of 1 to 30 represented by the above R ⁴ and R ⁵ . A group obtained by removing (n-1) hydrogen atoms from the same group as exemplified in the hydrocarbon group.

The aliphatic cyclic hydrocarbon group having 3 to 30 carbon atoms represented by the above R ⁶ is, for example, a cyclic hydrocarbon group having 3 to 30 carbon atoms represented by the above R ⁴ and R ⁵ A group in which (n-1) hydrogen atoms are removed from the same group as the exemplified group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by the above R ⁶ are exemplified by the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by the above R ⁴ and R ⁵ . A group in which (n-1) hydrogen atoms are removed from the same group.

Examples of the combination of two or more of these groups represented by the above-mentioned R ⁶ include two or more kinds of these groups which are represented by the above R ⁴ and R ⁵ . A group in which (n-1) hydrogen atoms are removed from the same group as the exemplified group.

The group represented by the R ⁴ to R ⁶ may be substituted. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, a n-butyl group, a tert-butyl group, a hydroxyl group, a carboxyl group, a halogen atom, and an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Further, examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

Examples of the compound represented by the formula (6) include a (cyclo)alkylamine compound, a nitrogen-containing heterocyclic compound, a guanamine group-containing compound, and a urea compound.

The (cyclo)alkylamine compound may, for example, be a compound having one nitrogen atom, a compound having two nitrogen atoms, or a compound having three or more nitrogen atoms.

Examples of the (cyclo)alkylamine compound having one nitrogen atom include mono (cyclo)alkanes such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, 1-aminodecane, and cyclohexylamine. Base amines; Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, Di(cyclo)alkylamines such as di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentane Amine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine, etc. (cyclo)alkylamines; a substituted alkylamine such as triethanolamine; Aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, N,N-dibutylaniline, 4-nitroaniline, Diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline, An aromatic amine such as 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane or 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane.

Examples of the (cyclo)alkylamine compound having two nitrogen atoms include ethylenediamine, tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, and 4,4'-di. Aminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenylamine, 2,2-double (4-Aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 1,4-bis[1-(4-aminophenyl)- 1-methylethyl]benzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene, bis(2-dimethylaminoethyl)ether, bis ( 2-diethylaminoethyl)ether, 1-(2-hydroxyethyl)-2-imidazolidinone, 2-quinazolidone, N,N,N',N'-tetrakis (2-hydroxypropyl) ) Ethylenediamine and the like.

Examples of the (cyclo)alkylamine compound having three or more nitrogen atoms include polymers such as polyethyleneimine, polyallylamine, and 2-dimethylaminoethyl acrylamide.

Examples of the nitrogen-containing heterocyclic compound include nitrogen-containing aromatic heterocyclic compounds. a compound, a nitrogen-containing aliphatic heterocyclic compound, or the like.

Examples of the nitrogen-containing aromatic heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, and 1-benzyl-2. -imidazoles such as methylimidazole and 1-benzyl-2-methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2- Phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-hydroxyquinoline, acridine Pyridine such as 2,2':6',2"-terridinyl.

Examples of the nitrogen-containing aliphatic heterocyclic compound include piperazines such as piperazine and 1-(2-hydroxyethyl)piperazine; pyrazine, pyrazole, pyridazine, anthracene, pyrrolidine, and valine. Piperidine, piperidine ethanol, 3-piperidinyl-1,2-propanediol, morpholine, 4-methylmorpholine, 1-(4-morpholinyl)ethanol, 4-ethylmercaptomorpholine, 3- (N-morpholinyl)-1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and the like.

Examples of the amide group-containing compound include N-tert-butoxycarbonyldi-n-octylamine, N-tert-butoxycarbonyldi-n-decylamine, and N-tert-butoxycarbonyldi- N-decylamine, N-tert-butoxycarbonyldicyclohexylamine, N-tert-butoxycarbonyl-1-adamantylamine, N-tert-butoxycarbonyl-2-adamantylamine, N - tert-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-(-)-1-(t-butoxycarbonyl)-2-pyrrolidinemethanol, (R)-( +)-1-(t-butoxycarbonyl)-2-pyrrolidinemethanol, N-tert-butoxycarbonyl-4-hydroxypiperidine, N-t-butoxycarbonylpyrrolidine, N- Tributoxycarbonylpiperazine, N,N-di-t-butoxycarbonyl-1-adamantylamine, N,N-di-t-butoxycarbonyl-N-methyl-1-adamantane Amine, N-tert-butoxycarbonyl-4,4'-diaminodiphenylmethane, N,N'-di-t-butoxycarbonylhexamethylenediamine, N,N,N ',N'-tetra-butoxycarbonylhexamethylenediamine, N,N'-di-t-butoxycarbonyl-1,7-diaminoheptane, N,N'-di -Tertibutoxycarbonyl-1,8-diaminooctane, N,N'-di-t-butoxycarbonyl-1,9-diaminodecane, N,N'-di- Tributoxycarbonyl-1,10-diaminodecane, N,N'-di-t-butoxycarbonyl-1,12-diaminododecane, N,N'-di-third Butoxycarbonyl-4,4'-diaminodiphenylmethane, N-tert-butoxycarbonylbenzimidazole, N-tert-butoxycarbonyl-2-methylbenzimidazole, N- N-tert-butoxycarbonyl-containing amine compound such as tributoxycarbonyl-2-phenylbenzimidazole; formamide, N-methylformamide, N,N-dimethylformamide , acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-B 1-adamantyl amine group, iso-cyanuric acid tris (2-hydroxyethyl) acrylate.

Examples of the urea compound include urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and 1,3-di Phenylurea, tri-n-butyl thiourea, and the like.

Among these, a (cyclo)alkylamine compound, a nitrogen-containing aliphatic heterocyclic compound, and more preferably 1-aminodecane, di-n-octylamine, tri-n-octylamine, tetramethyl B are preferable. Diamine, N,N-dibutylaniline, valine.

As a suitable form of the nitrogen-containing compound, it is preferred to contain a plurality (2 a nitrogen-containing compound of a nitrogen atom (a polyvalent nitrogen-containing compound). In particular, it is preferably a form containing three or more nitrogen atoms, and more preferably a form containing four or more nitrogen atoms.

In addition, as another suitable form of the nitrogen-containing compound, the compound represented by the formula (3) is exemplified as being more excellent in the effect of the present invention.

In the formula (3), A represents a single bond or an n-valent organic group.

n represents an integer of 2 or more.

Specific examples of A include a single bond, a group represented by the following formula (1A), and a group represented by the following formula (1B). -NH-, -NR _W -, -O-, -S-, carbonyl, alkylene, alkenyl, alkynyl, cycloalkyl, aromatic, heterocyclic, and A group of n-valent organic groups having a combination of the above is preferred. Here, in the formula, R _W represents an organic group, preferably an alkyl group, an alkylcarbonyl group or an alkylsulfonyl group. Further, in the combination, the hetero atoms are not linked to each other.

Among them, an aliphatic hydrocarbon group (alkylene group, alkenyl group, alkynylene group, and cycloalkyl group), a group represented by the formula (1B), -NH-, -NR _W - are preferable.

Here, as the alkyl group, the alkenyl group, and the alkynylene group, the carbon number is preferably from 1 to 40, more preferably from 1 to 20 carbon atoms, and even more preferably from 2 to 12 carbon atoms. The alkylene group may be a straight chain, may be branched, and may have a substituent. Here, as the cycloalkyl group, the carbon number is preferably 3 to 40, more preferably 3 to 20 carbon atoms, and still more preferably 5 to 12 carbon atoms. The cycloalkyl group may be a single ring or a polycyclic ring and may have a substituent on the ring.

The aromatic group may be a single ring or a polycyclic ring, and may also contain a non-benzene aromatic group. Examples of the monocyclic aromatic group include a benzene residue, a pyrrole residue, a furan residue, a thiophene residue, and an anthracene residue. Examples of the polycyclic aromatic group include a naphthalene residue and an anthracene residue. Examples of the fused tetraphenyl residue, the benzofuran residue, the benzothiophene residue and the like are exemplified. The aromatic group may have a substituent.

The n-valent organic group may have a substituent, and the kind thereof is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkenyl group, an alkenyloxy group, and an alkenyl group. Carbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, aralkyl, aralkoxy, aralkyl A carbonyl group, an aralkylcarbonyloxy group, an aralkyloxycarbonyl group, a hydroxyl group, a decylamino group, a carboxyl group, a cyano group, a fluorine atom or the like is exemplified.

B represents a single bond, an alkylene group, a cycloalkyl group, or an aromatic group, and the alkylene group, the extended cycloalkyl group, and the aromatic group may have a substituent. Here, the description of the alkyl group, the cycloalkyl group, and the aromatic group is the same as described above.

However, A and B are not all single keys.

Rz each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may contain a hetero atom, or an aromatic hydrocarbon group which may contain a hetero atom.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but from the viewpoint of further excellent effects of the present invention, it is preferably from 1 to 20, more preferably from 1 to 10.

Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

The aliphatic hydrocarbon group and the aromatic hydrocarbon group may also contain a hetero atom. The definition and suitable form of the hetero atom are the same as the definition and suitable form of the hetero atom described in the formula (1-1).

Further, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may further contain a substituent (for example, a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, a pendant oxy group, an alkoxy group, or a halogen atom). ).

n is preferably an integer of 2 to 8, and more preferably an integer of 3 to 8.

Further, the compound represented by the formula (3) preferably has three or more nitrogen atoms. In this form, when n is 2, at least one nitrogen atom is contained in A. The A atom contains a nitrogen atom, and for example, A contains at least one selected from the group consisting of a group represented by the formula (1B), -NH-, and -NR _W -.

Hereinafter, the compound represented by the formula (3) is exemplified.

[Chemistry 19]

(phosphorus compound)

The phosphorus compound refers to a compound containing -P<(phosphorus atom). Further, the phosphonium compound does not contain a phosphonium salt compound. The phosphorus-based compound mainly forms an interaction between the phosphorus atom in the compound and the polar group. For example, when the polar group is a carboxyl group, it interacts with a phosphorus atom in the phosphorus compound to form a salt.

The phosphorus-based compound may contain at least one phosphorus atom, and may contain plural (two or more).

The molecular weight of the phosphorus-based compound is not particularly limited, but from the viewpoint of further excellent effects of the present invention, it is preferably from 70 to 500, more preferably from 70 to 300.

The preferable form of the phosphorus-based compound is preferably a compound represented by the following formula (4-1) and a compound represented by the formula (4-2) from the viewpoint that the effect of the present invention is more excellent. Phosphorus compounds in the group formed.

In the formula (4-1) and the formula (4-2), R _{W is} independently selected from an aliphatic hydrocarbon group which may contain a hetero atom, an aromatic hydrocarbon group which may contain a hetero atom, or a combination of two or more of these. The base in the group consisting of the bases.

The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic chain. Further, the number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but from the viewpoint of further excellent effects of the present invention, it is preferably from 1 to 15, more preferably from 1 to 5.

Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkene group, an alkyne group, or a combination of two or more of these.

The number of carbon atoms contained in the aromatic hydrocarbon group is not particularly limited, but from the viewpoint of further excellent effects of the present invention, it is preferably 6 to 20, more preferably 6 to 10.

Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

A hetero atom may also be contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group. The definition and suitable form of the hetero atom are the same as the definition and suitable form of the hetero atom described in the formula (1-1). Further, it is preferred to contain an oxygen atom as a hetero atom, and it is preferably contained in the form of -O-.

L _W represents a divalent linking group. The divalent linking group may, for example, be a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having a carbon number of 1 to 8. For example, an alkylene group such as a methylene group, an ethyl group or a propyl group). a substituted or unsubstituted divalent aromatic hydrocarbon group (preferably having a carbon number of 6 to 12, such as an extended aryl group), -O-, -S-, -SO ₂ -, -N(R) -(R:alkyl), -CO-, -NH-, -COO-, -CONH-, or a combination of two or more of these (for example, an alkoxy group, an alkoxycarbonyl group, Alkyl carbonyloxy group, etc.).

Among them, from the viewpoint of more excellent effects of the present invention, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group is preferred.

Specific examples of the phosphorus compound are exemplified below.

[Chem. 21]

As described above, the compound (A) may be in the form of a low molecular compound or in the form of a polymer compound. However, from the viewpoint of multi-point interaction with a polar group, a form of a polymer compound is preferred.

Hereinafter, the form of the polymer compound in the onium salt compound, the nitrogen-containing compound, and the phosphorus-based compound will be described in detail.

(鎓 salt compound)

The form of the polymer compound in the onium salt compound is exemplified by a polymer having a phosphonium salt. The polymer having a phosphonium salt refers to a polymer having a phosphonium salt structure in a side chain or a main chain. In particular, a polymer containing a repeating unit having a phosphonium salt structure is preferred.

The definition of the phosphonium salt structure is as described above, as is the definition of the cation and anion.

A suitable form of the polymer having a phosphonium salt is a polymer containing a repeating unit represented by the formula (5-1) from the viewpoint of further excellent effects of the present invention.

In the formula (5-1), R _p represents a hydrogen atom or an alkyl group. The number of carbon atoms contained in the alkyl group is not particularly limited, but from the viewpoint of further excellent effects of the present invention, it is preferably from 1 to 20, more preferably from 1 to 10.

L _p represents a divalent linking group. The definition of the divalent linking group represented by L _p is the same as the definition of L represented by the above formula (1-2).

In view of the fact that the effect of the present invention is more excellent, L _{p is} preferably an alkyl group, an aryl group, a -COO- group, and a combination of two or more of these groups (- Alkyl-alkyl-, -COO-alkylene-, etc.), more preferably an alkylene group.

A _p represents a group having a phosphonium salt structure, and specifically, it is preferably a residue obtained by removing one hydrogen atom from the onium salt represented by any one of free formula (1-1) and formula (1-2). base. Furthermore, the term residues refers to the removal of one hydrogen atom from the onium salts represented by any of structural formulas in position, and bonded to the base structure on the L _p. Usually, one hydrogen atom in R is removed and can be bonded to the group of the structure on the L _p .

The definition of each group in the formula (1-1) and the formula (1-2) is as described above.

The content of the repeating unit represented by the above formula (5-1) in the polymer is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferable with respect to all the repeating units in the polymer. It is 30% by mole to 100% by mole, more preferably 50% by mole to 100% by mole.

The weight average molecular weight of the polymer is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably from 1,000 to 30,000, more preferably from 1,000 to 10,000.

The weight average molecular weight and the degree of dispersion (weight average molecular weight / number average molecular weight) of the polymer are defined as polystyrene-converted values obtained by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight and the degree of dispersion can be obtained, for example, by using HLC-8120 (manufactured by Tosoh Co., Ltd.) and TSK gel Multipore HXL-M (Tosoh Corporation) Manufactured, 7.8 mm inner diameter (Inner Diameter, ID) × 30.0 cm) was used as a column, and tetrahydrofuran (THF) was used as a solution.

As a suitable form of the repeating unit represented by the formula (5-1), it can be listed The repeating unit represented by the formula (5-2) is given.

In the formula (5-2), R, R _p , L _p , and X ^- are as defined above.

Further, as a suitable form of the repeating unit represented by the formula (5-2), a repeating unit represented by the formula (5-3) to the formula (5-5) can be mentioned.

In the formula (5-3), R, R _p and X ^- are as defined above.

In the formula (5-4), R, R _p and X ^- are as defined above.

A represents -O-, -NH-, or -NR-. The definition of R is the same as the definition of R in the formula (1-1).

B represents an alkylene group.

In the formula (5-5), R, R _p and X ^- are as defined above.

(nitrogen-containing compounds)

The form of the polymer compound in the nitrogen-containing compound is preferably a polymer having an amine group from the viewpoint of further excellent effects of the present invention. In the present specification, the term "amino group" means a concept including a primary amino group, a secondary amine group, and a tertiary amine group. Further, the secondary amine group also includes a cyclic secondary amine group such as a pyrrolidinyl group, a piperidinyl group, a piperazinyl group or a hexahydrotriazinyl group.

The amine group can be included in any of the main chain and side chains of the polymer.

Specific examples of the side chain when the amine group is contained in a part of the side chain are shown below. Further, * indicates a connection portion with a polymer and/or an oligomer residue.

[化25]

[化27]

Examples of the polymer having the amine group include polyallylamine, polyethyleneimine, polyvinylpyridine, polyvinylimidazole, polypyrimidine, polytriazole, polyquinoline, polyfluorene, and Polyfluorene, polyvinylpyrrolidone, polybenzimidazole, and the like.

A suitable form of the polymer having an amine group is a polymer having a repeating unit represented by the formula (2).

In the formula (2), R ¹ represents a hydrogen atom or an alkyl group. The number of carbon atoms contained in the alkyl group is not particularly limited, but from the viewpoint of further excellent effects of the present invention, it is preferably from 1 to 4, more preferably from one to two.

R ² and R ³ each independently represent a hydrogen atom, an alkyl group which may contain a hetero atom, a cycloalkyl group which may contain a hetero atom, or an aromatic group which may contain a hetero atom.

The number of carbon atoms contained in the alkyl group and the cycloalkyl group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10.

Examples of the aromatic group include an aromatic hydrocarbon group or an aromatic heterocyclic group.

The alkyl group, the cycloalkyl group, and the aromatic group may further contain a hetero atom. The definition and suitable form of the hetero atom are the same as the definition and suitable form of the hetero atom described in the formula (1-1).

Further, the alkyl group, the cycloalkyl group, and the aromatic group may further contain a substituent (for example, a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, or a pendant oxy group), and an alkane. Oxyl, halogen atom).

L _a represents a divalent linking group. Definition of a divalent linking group represented by L _a and L is defined by the formula (1-2) is the same.

In view of the fact that the effect of the present invention is more excellent, L _{a is} preferably an alkyl group, an extended aryl group, a -COO- group, and a combination of two or more of these. Alkyl-alkyl-, -COO-alkylene-, etc.), more preferably an alkylene group.

Further, in the group, and the divalent linking group represented by L _a indicated by the R ¹ ~ R ³ are represented, may be further substituted with a substituent group (e.g., hydroxyl group).

Hereinafter, the repeating unit represented by the formula (2) is exemplified.

[化30]

[化31]

The content of the repeating unit represented by the above formula (2) in the polymer is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 40 with respect to all the repeating units in the polymer. Molar%~100% by mole, more preferably 70% by mole to 100% by mole.

Further, the polymer may further contain a repeating unit other than the repeating unit represented by the formula (2).

The weight average molecular weight of the polymer having an amine group is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably from 1,000 to 30,000, more preferably from 1,000 to 10,000.

The compound (A) is not particularly limited as long as it interacts with a polar group, but is preferably a basic compound. In the present invention, the term "basic compound" means a polar group contained in a resin in a photosensitive ray-sensitive or radiation-sensitive resin composition by an acid-base interaction, for example, a -COOH moiety, more specifically a compound which forms a salt corresponding to a repeating unit of a methacrylic acid structure, specifically, The nitrogen-containing compound is listed.

The surface treatment agent is not particularly limited as long as it contains the compound (A), but preferably contains a resin containing a repeating unit having a basic functional group as a basic compound. Further, the basic compound preferably contains at least one selected from the group consisting of a tertiary amino group, a quaternary ammonium group, and a heteroaryl group which may have a substituent and have a nitrogen atom as a ring member.

Further, the compound (A) is preferably a developer containing an organic solvent which is soluble in the step (5A) or the step (5B), and examples thereof include a nonionic low molecular compound and a resin, and specifically, Preferable examples thereof include triethylamine, trioctylamine, pyridine, N,N,N',N'-tetramethylethylenediamine, poly(dimethylaminoethyl (meth)acrylate), and the like.

When the surface treatment agent contains a solvent, specific examples and preferred examples of the solvent are substantially the same as those of the specific examples and preferred examples of the eluent, and it is particularly preferable to use the contact sensitizing ray or sensitizing radiation as a solvent. The film dissolution rate at 23 ° C in the case of the unexposed coating film of the film is 0.1 nm / s or less.

Specifically, an alcohol solvent or an ether solvent is preferred. Specific examples thereof include an alkyl group having 3 or more carbon atoms (more preferably 5 or more and 10 or less carbon atoms), a cycloalkyl group (preferably having a carbon number of 5 or more and 10 or less), and an aralkyl group. An alcohol (dialkyl ether or the like) of at least one of a group (preferably having a carbon number of 7 or more and 10 or less). In addition, water can also be used as a solvent.

The film dissolution rate indicates the amount of decrease in film thickness per unit time when the solution is brought into contact with the sensitizing ray-sensitive or radiation-sensitive film. Membrane dissolution rate is as follows Dissolution rate (reduction rate of film thickness): After forming a sensitizing ray-sensitive or radiation-sensitive film on a substrate, it is measured at room temperature using a Quartz Crystal Microbalance (QCM) sensor or the like (23). The average dissolution rate (the rate of decrease in film thickness) of the film when immersed in the developer for 1000 seconds at ° C).

<Photosensitized ray-sensitive or radiation-sensitive resin composition>

The composition of the present invention (hereinafter also referred to as a first sensitizing ray-sensitive or radiation-sensitive resin composition) contains a resin which is decomposed by the action of an acid to generate a polar group.

Further, in one embodiment, the composition of the present invention may further contain at least one of a compound which generates an acid by irradiation with actinic rays or radiation, a hydrophobic resin, a basic compound, and a surfactant.

Hereinafter, each component will be described.

[Resin which decomposes due to the action of acid and produces a polar group]

A resin which decomposes due to the action of an acid and which generates a polar group (hereinafter also referred to as "resin (A)") is a resin which changes in polarity due to the action of an acid, and is developed by an action of an acid for an organic solvent system. The solubility of the liquid is reduced, and the solubility of the alkaline developer is increased.

The resin (A) preferably has a group which decomposes due to the action of an acid and generates a polar group in the main chain or the side chain of the resin or both the main chain and the side chain (hereinafter, also referred to as "acid-decomposable group"). ).

The acid-decomposable group is preferably a structure having a group in which a polar group is decomposed and desorbed by the action of an acid.

As a polar group, as long as it is insoluble or insoluble in development containing an organic solvent The group in the liquid is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonylamino group, and a sulfonyl group. Amine, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)indolylene, bis(alkylcarbonyl)methylene, bis(alkyl Carbonyl) fluorenylene, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl) fluorenylene, tris(alkylcarbonyl)methylene, tris(alkylsulfonyl) An acidic group such as a methylene group (a group which is dissociated in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide as a developing solution previously used as a resist), or an alcoholic hydroxyl group or the like.

In addition, the term "alcoholic hydroxyl group" means a hydroxyl group bonded to a hydrocarbon group, and means a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and the α-position of a hydroxyl group is pulled by a fluorine atom or the like. The radically substituted aliphatic alcohol group (for example, a fluorinated alcohol group (hexafluoroisopropanol group, etc.)) is excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.

Preferred examples of the polar group include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

A group which is preferably an acid-decomposable group is a group obtained by substituting a hydrogen atom of the group by a group which is desorbed by an acid.

Examples of the group which is desorbed by the acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R ₀₁ )(R). ₀₂ ) (OR ₃₉ ) and so on.

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

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms.

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be a monocyclic type or a polycyclic type. A cycloalkyl group having a carbon number of 3 to 20 is preferred.

The aryl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms.

The aralkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms.

The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms.

The ring formed by bonding R ₃₆ and R _{37 is} preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecylalkyl group, a tetracyclododecyl group or an adamantyl group. More preferably, it is a monocyclic cycloalkyl group having 5 to 6 carbon atoms, particularly preferably a monocyclic cycloalkyl group having 5 carbon atoms.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group or a tertiary alkyl ester group. More preferably, it is a tertiary alkyl ester group.

[Repeating unit having an acid-decomposable group]

The resin (A) preferably contains a repeating unit having an acid-decomposable group.

In one embodiment, the resin (A) preferably contains a repeating unit (AI) which is decomposed by an acid to generate a carboxyl group (hereinafter also referred to as "repeating unit (AI)") as a repeating unit having an acid-decomposable group. More preferably, it contains a repeating unit represented by the following general formula (aI) or general formula (aI').

[化32]

In the general formula (aI) and the general formula (aI'), Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

T represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a ring structure. Further, the ring structure may contain a hetero atom such as an oxygen atom in the ring.

Examples of the divalent linking group of T include an alkylene group, a —COO—Rt— group, a —O—Rt— group, and a phenylene group. In the formula, Rt represents an alkylene group or a cycloalkyl group.

From the viewpoint of the insolubility of the resist to the organic solvent-based developer, T in the formula (aI) is preferably a single bond or a -COO-Rt- group, and more preferably a -COO-Rt- group. Rt is preferably an alkylene group having a carbon number of 1 to 5, more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group.

T in the formula (aI') is preferably a single bond.

The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

The alkyl group of Xa ₁ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

Xa _{1 is} preferably a hydrogen atom or a methyl group.

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched.

The cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantane. A polycyclic cycloalkyl group such as a polycyclic group.

The ring structure formed by the two bonds of Rx ₁ , Rx ₂ and Rx ₃ is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring or a cyclohexyl ring, a norbornane ring or a tetracyclodecane ring. A polycyclic cycloalkane group such as a tetracyclododecane ring or an adamantane ring. Particularly preferred is a monocyclic cycloalkane ring having a carbon number of 5 or 6.

Rx ₁ , Rx ₂ and Rx ₃ are each independently an alkyl group, more preferably a linear or branched alkyl group having a carbon number of 1 to 4.

Each of the groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a cycloalkyl group (having a carbon number of 3 to 8), a halogen atom, and an alkoxy group (having a carbon number of 1). ~4), a carboxyl group, an alkoxycarbonyl group (having a carbon number of 2 to 6), etc., preferably having a carbon number of 8 or less. In addition, from the viewpoint of further improving the dissolution contrast of the developer containing the organic solvent before and after the acid decomposition, it is more preferably a substituent having no hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom (for example, more preferably not The alkyl group substituted by a hydroxyl group, etc.) is more preferably a group containing only a hydrogen atom and a carbon atom, and particularly preferably a linear or branched alkyl group or a cycloalkyl group.

Specific examples of the repeating unit represented by the general formula (aI) or the general formula (aI') are listed below, but the present invention is not limited to these specific examples.

In a specific example, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Z represents a substituent, and when a plurality of Z are present, a plurality of Zs may be the same or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as those of the specific examples and preferred examples of the substituents which each of Rx ₁ to Rx ₃ may have.

[化34]

[化36]

[化38]

In the following specific examples, Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

[39]

In one embodiment, the resin (A) is preferably a repeating unit having an acid-decomposable group in a total of 4 to 9 repeating units having a carbon number in a portion decomposed by an acid. More preferably, in the above formula (aI), the carbon number of the -C(Rx ₁ )(Rx ₂ )(Rx ₃ ) moiety is from 4 to 9.

More preferably, in the general formula (aI), Rx ₁ , Rx ₂ and Rx ₃ are each a methyl group or an ethyl group, or a form represented by the following formula (aII).

In the formula (aII), R ₃₁ represents a hydrogen atom or an alkyl group.

R ₃₂ represents a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a second butyl group.

R ₃₃ represents an atomic group required to form a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded. A part of the carbon atoms constituting the ring of the alicyclic hydrocarbon structure may also be substituted by a hetero atom or a group having a hetero atom.

Here, the total of the carbon atoms of R ₃₂ and R ₃₃ is 8 or less.

The alkyl group of R ₃₁ may have a substituent, and examples of the substituent include a fluorine atom, a hydroxyl group and the like.

R ₃₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R _{32 is} preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group, more preferably a methyl group or an ethyl group.

The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with a carbon atom is preferably a 3-membered ring to an 8-membered ring, more preferably a 5-membered ring or a 6-membered ring.

In the monocyclic alicyclic hydrocarbon structure in which R _{33 is} formed together with a carbon atom, examples of the hetero atom which can form a ring include an oxygen atom and a sulfur atom, and examples of the group having a hetero atom include a carbonyl group. However, the group having a hetero atom is preferably not an ester group (ester bond).

The monocyclic alicyclic hydrocarbon structure in which R _{33 is} formed together with a carbon atom is preferably formed only of a carbon atom and a hydrogen atom.

Further, in another embodiment, the resin (A) may further contain a repeating unit (aIII) as a repeating unit having an acid-decomposable group: the number of carbon atoms decomposed by the acid is 10 to 20, and includes The acid decomposition site of the polycyclic structure.

The repeating unit (aIII) having 10 to 20 carbon atoms in the acid decomposition site and having a polycyclic structure in the acid decomposition site is preferably Rx ₁ and Rx ₂ in the above formula (aI). One of Rx ₃ is a group having an adamantane skeleton, and the remaining two are in the form of a linear or branched alkyl group; or in the formula (aI), two of Rx ₁ , Rx ₂ and Rx ₃ are bonded The adamantane structure is formed, and the remaining one is in the form of a linear or branched alkyl group.

Further, the resin (A) may further contain a repeating unit which is decomposed by an action of an acid and which produces an alcoholic hydroxyl group, as shown below, as a repeating unit having an acid-decomposable group.

In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

[化41]

The number of repeating units having an acid-decomposable group which may be contained in the resin (A) may be one type or two or more types may be used in combination.

When the resin (A) contains two or more kinds of repeating units having an acid-decomposable group, for example, in the above formula (aI), Rx ₁ , Rx ₂ and Rx ₃ are all in the form of a methyl group or an ethyl group. Or a repeating unit of the form represented by the above formula (aII) and a repeating unit (aIII) having 10 to 20 carbon atoms in the acid decomposition site and having a polycyclic structure in the acid decomposition site A combination of repeated units represented.

In the following, a preferred combination of the two types of the repeating unit having two or more acid-decomposable groups is included in the resin (A), but the present invention is not limited thereto.

[化43]

The total amount of the repeating unit having an acid-decomposable group is preferably from 30 mol% to 80 mol%, more preferably from 40 mol% to 75 mol%, based on all the repeating units constituting the resin (A). The optimum is 45% by mole to 70% by mole, and the best is 50% by mole to 70% by mole.

With respect to all the repeating units constituting the resin (A), the general formula (aI) The content of the repeating unit represented is preferably from 30 mol% to 80 mol%, more preferably from 40 mol% to 75 mol%, particularly preferably from 45 mol% to 70 mol%, most preferably 50% by mole %~70% by mole.

Further, the proportion of the repeating unit (aIII) in all the repeating units having an acid-decomposable group is preferably from 3 mol% to 50 mol%, more preferably from 5 mol% to 40 mol%, most preferably It is 5 mol% to 30 mol% or less.

[Repeating unit having a lactone structure or a sultone structure]

The resin (A) may also contain a repeating unit having a lactone structure or a sultone structure.

As the lactone structure or the sultone structure, any one may be used as long as it has a lactone structure or a sultone structure, but it is preferably a 5-membered ring lactone structure to a 7-membered ring lactone structure or a 5-membered ring sulfone. The structure of the ester structure is up to 7-membered ring sultone structure, and more preferably the other ring structure is formed into a bicyclic structure or a spiro structure, and is formed by shrinking a ring in a 5-membered ring lactone structure to a 7-membered ring lactone structure, or the like. The ring structure is formed by condensing a ring in a 5-membered sultone structure to a 7-membered sultone structure in a form of a bicyclic structure or a spiro structure. Furthermore, it is more preferable to contain a lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-21) or a general formula (SL1-1) to general formula ( A repeating unit of the sultone structure represented by any of SL1-3). Alternatively, the lactone structure or the sultone structure can be directly bonded to the backbone. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), The preferred lactone structure is (LC1-4). By using this specific lactone structure, Line Edge Roughness (LER), development defects Becomes good.

The lactone moiety or the sultone moiety may have a substituent (Rb ₂ ) or may have no substituent (Rb ₂ ). Preferred examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a carbon number of 2 Alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group or the like of ～8. More preferably, it is an alkyl group having a carbon number of 1 to 4, a cyano group, or an acid-decomposable group. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

The repeating unit having a lactone structure or a sultone structure usually has an optical isomer, and any optical isomer can be used. Further, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When one optical isomer is mainly used, its optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more.

The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following formula (III).

In the above formula (III), A represents an ester bond (a group represented by -COO-) or a guanamine bond (a group represented by -CONH-).

When a plurality of R ₀ are present, respectively, an alkylene group, a cycloalkyl group, or a combination thereof is independently represented.

When a plurality of Z are present, respectively, a single bond, an ether bond, an ester bond, and a guanamine are independently represented. Bond, urethane bond

Urea bond

Here, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.

n is the number of repetitions of the structure represented by -R ₀ -Z-, and represents an integer of 0 to 5, preferably 0 or 1, more preferably 0. When n is 0, -R ₀ -Z- does not exist and becomes a single bond.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and the cycloalkyl group of R ₀ may have a substituent.

Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group of R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group.

The alkyl group and the cycloalkyl group of R _{0 and} the alkyl group of R ₇ may be substituted, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom or a mercapto group, a hydroxyl group or an alkoxy group. .

R _{7 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The preferred chain alkyl group in R ₀ is preferably a chain alkyl group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an exoethyl group, and a propyl group. The cycloalkylene group is preferably a cycloalkyl group having a carbon number of 3 to 20, and examples thereof include a cyclohexylene group, a cyclopentylene group, an extended borneol group, and an adenantyl group. In order to exhibit the effects of the present invention, a chain alkyl group is more preferred, and a methylene group is particularly preferred.

The monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure, and specific examples thereof include a general formula (LC1-1). a lactone structure or a sultone structure represented by any one of the formula (LC1-21) and the formula (SL1-1) to the formula (SL1-3), among which The structure represented by (LC1-4). Further, it is more preferable that n ₂ in (LC1-1) to (LC1-21) is 2 or less.

Further, R _{8 is} preferably a monovalent organic group having an unsubstituted lactone structure or a sultone structure, or a lactone structure or a sulfone having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. The monovalent organic group of the ester structure is more preferably a monovalent organic group having a lactone structure (cyanolactone) containing a cyano group as a substituent.

Specific examples of the repeating unit containing a group having a lactone structure or a sultone structure are shown below, but the present invention is not limited thereto.

[48]

[化49]

[化50]

In order to enhance the effect of the present invention, two or more kinds of repeating units having a lactone structure or a sultone structure may be used in combination.

When the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is preferably 5 with respect to all the repeating units in the resin (A). Mohr%~60% by mole, more preferably 5% by mole to 55% by mole, and even more preferably 10% by mole to 50% by mole.

[Repeating unit having a cyclic carbonate structure]

Further, the resin (A) may also contain a repeating unit having a cyclic carbonate structure.

The repeating unit having a cyclic carbonate structure is preferably represented by the following formula (A-1) Representation of repeating units.

In the formula (A-1), R _A ¹ represents a hydrogen atom or an alkyl group.

When n is 2 or more, R _A ² each independently represents a substituent.

A represents a single bond or a divalent linking group.

Z represents an atomic group which forms a monocyclic structure or a polycyclic structure together with a group represented by -O-C(=O)-O- in the formula.

n represents an integer of 0 or more.

The general formula (A-1) will be described in detail.

The alkyl group represented by R _A ¹ may have a substituent and a fluorine atom. R _A ¹ preferably represents a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably represents a methyl group.

The substituent represented by R _A ² is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amine group or an alkoxycarbonylamino group. The alkyl group having 1 to 5 carbon atoms is preferably a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms. The alkyl group may have a substituent such as a hydroxyl group.

n is an integer of 0 or more indicating the number of substituents. n is, for example, preferably 0 to 4, more preferably 0.

Examples of the divalent linking group represented by A include an alkylene group, a cycloalkyl group, an ester bond, a guanamine bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. Wait. The alkylene group is preferably an alkylene group having a carbon number of 1 to 10, more preferably an alkylene group having a carbon number of 1 to 5.

In one embodiment of the invention, A is preferably a single bond or an alkylene group.

The monocyclic ring containing -OC(=O)-O- represented by Z is, for example, a cyclic carbonate represented by the following general formula (a), and 5 members of n _A = 2 to 4 Ring ~ 7 member ring, preferably 5 member ring or 6 member ring (n _A = 2 or 3), more preferably 5 member ring (n _A = 2).

Examples of the polycyclic ring containing -OC(=O)-O- represented by Z include a cyclic carbonate represented by the following formula (a) together with one or two or more other ring structures. A structure forming a condensed ring or a structure forming a spiro ring. The "other ring structure" which can form a condensed ring or a spiro ring may be an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring.

[化52]

In the resin (A), one type of the repeating unit represented by the formula (A-1) may be contained alone, or two or more types may be contained.

In the resin (A), the content of the repeating unit having a cyclic carbonate structure (preferably the repeating unit represented by the formula (A-1)) is higher than that of all the repeating units constituting the resin (A). Good for 3 moles % ~ 80 mole %, more preferably 3 mole % ~ 60 mole %, especially good 3 mole % ~ 30 mole %, best 10 mole % ~ 15 mole % . By setting such a content ratio, developability as a resist, low defect, low LWR, low PEB temperature dependency, profile, and the like can be improved.

Specific examples of the repeating unit represented by the general formula (A-1) are listed below, but the present invention is not limited to these specific examples.

Moreover, the meaning of the general formula (A-1) in the following specific examples in R _A ¹ R _A ¹ same.

[化53]

[repeating unit having a hydroxyl group, a cyano group or a carbonyl group]

The resin (A) may also contain a repeating unit having a hydroxyl group, a cyano group or a carbonyl group. Thereby, the substrate adhesion and the developer affinity are improved.

The repeating unit having a hydroxyl group, a cyano group or a carbonyl group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group, and preferably has no acid-decomposable group.

Further, the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group is preferably different from the repeating unit having an acid-decomposable group (i.e., a repeating unit which is stable to an acid).

The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by a hydroxyl group, a cyano group or a carbonyl group is preferably an adamantyl group, a diadamantyl group or a norbornyl group.

More preferably, it is a repeating unit represented by any one of the following general formulas (AIIa) to (AIIe).

In the formula, Rx represents a hydrogen atom, a methyl group, a methylol group, or a trifluoromethyl group.

Ab represents a single bond or a divalent linking group.

Examples of the divalent linking group represented by Ab include an alkyl group and a stretching group. A cycloalkyl group, an ester bond, a guanamine bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylidene group, and a propyl group.

In one embodiment of the invention, the Ab is preferably a single bond or an alkylene group.

Rp represents a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. The plurality of Rp may be the same or different, and at least one of the plurality of Rp represents a hydroxyl group or a hydroxyalkyl group.

The resin (A) may contain a repeating unit having a hydroxyl group, a cyano group or a carbonyl group, or may not contain a repeating unit having a hydroxyl group, a cyano group or a carbonyl group, and when the resin (A) contains a repeating unit having a hydroxyl group, a cyano group or a carbonyl group, The content of the repeating unit having a hydroxyl group, a cyano group or a carbonyl group in all the repeating units in the resin (A) is preferably from 1 mol% to 40 mol%, more preferably from 3 mol% to 30 mol%, More preferably, it is 5 mol% to 25 mol%.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these specific examples.

Further, a monomer described later in [0011] of the specification of International Publication No. 2011/122336 or a repeating unit corresponding thereto may be suitably used.

[repeating unit having an acid group]

The resin (A) may also contain a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonylamino group, a sulfonyl fluorenylene group, a bis-sulfonyl fluorenylene group, a naphthol structure, and an aliphatic alcohol group substituted at the α-position electron group (for example, hexafluoro group). Isopropanol group), more preferably contains a repeating unit having a carboxyl group. By containing a repeating unit having an acid group, the resolution in the use of the contact hole is increased. As a repeating unit having an acid group, it is preferred a repeating unit in which an acid group is directly bonded to a main chain of the resin as a repeating unit formed of acrylic acid or methacrylic acid, or a repeating unit in which an acid group is bonded to a main chain of the resin via a linking group, And a polymerization initiator or a chain transfer agent having an acid group to be introduced into the terminal of the polymer chain at the time of polymerization, and the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. Particularly preferred is a repeating unit formed of acrylic acid or methacrylic acid.

The resin (A) may contain a repeating unit having an acid group, or may not contain a repeating unit having an acid group, and when it contains a repeating unit having an acid group, has an acid group repeat with respect to all the repeating units in the resin (A) The content of the unit is preferably 25 mol% or less, more preferably 20 mol% or less. When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin (A) is usually 1 mol% or more.

Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.

In a specific example, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

[化59]

[Repeating unit having an alicyclic hydrocarbon structure containing no polar group and exhibiting no acid decomposition property]

The resin (A) in the present invention may further contain a repeating unit having an alicyclic hydrocarbon structure containing no polar group (for example, the acid group, a hydroxyl group, or a cyano group) and exhibiting no acid decomposition property. . Thereby, the elution of the low molecular component from the resist film into the liquid immersion liquid can be reduced during the immersion exposure, and the solubility of the resin can be appropriately adjusted when developing the developer containing the organic solvent. As such a repeating unit, A repeating unit represented by the formula (IV) can be cited.

In the formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.

Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. Ra is preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

The cyclic structure of R ₅ may include a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having a carbon number of 3 to 12 such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group, and a cycloalkenyl group having a carbon number of 3 to 12 such as a cyclohexenyl group. . A preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group contains a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the cyclic hydrocarbon group include a dicyclohexyl group, a perhydronaphthyl group and the like. Examples of the crosslinked cyclic hydrocarbon ring include decane, borneane, norbornane, norbornane, and bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring. And other bicyclic hydrocarbon rings, and tricyclo [5.2.1.0 ^3,8 ]nonane (Homobrendane), adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[4.3.1.1 ^{2, 5} ] tricyclic hydrocarbon ring such as undecane ring, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane, perhydro-1,4-bridged methylene-5,8-bridge A tetracyclic hydrocarbon ring such as a methylnaphthalene ring or the like. In addition, the cross-linked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydrohydroquinone, perhydrophenanthrene, perhydrohydroquinone, perhydrohydroquinone, perhydrohydroquinone, perhydroanthracene ring. A condensed ring obtained by condensing a plurality of 5-membered cycloalkane rings to 8 membered cycloalkane rings.

Preferred examples of the crosslinked cyclic hydrocarbon ring group include a norbornyl group, an adamantyl group, a bicyclooctyl group, and a tricyclo[5.2.1.0 ^2,6 ]decyl group. As a more preferable crosslinked cyclic hydrocarbon ring group, a norbornyl group and an adamantyl group are mentioned.

These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amine group substituted with a hydrogen atom.

The resin (A) may contain a repeating unit having an alicyclic hydrocarbon structure containing no polar group and exhibiting no acid decomposition property, or may not contain the repeating unit, and when the resin (A) contains the repeating unit, it is relative to the resin ( The content of the repeating unit in all repeating units in A) is preferably from 1 mol% to 50 mol%, more preferably from 5 mol% to 50 mol%, and even more preferably from 5 mol% to 30 mol. ear%.

Specific examples of the repeating unit having a polar group-free alicyclic hydrocarbon structure and exhibiting no acid decomposition property are listed below, but the present invention is not limited to these specific examples. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[化62]

[repeating unit with aromatic ring]

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 resin (A) preferably contains a repeating unit such as a hydroxystyrene unit. a repeating unit having an aromatic ring.

In one embodiment, the resin (A) may be in a form in which a structure corresponding to an acid generator described later is carried. Specifically, the structure described in JP-A-2011-248019 (particularly the structure described in paragraphs 0164 to 0191 and the resin described in the example of paragraph 0555) The structure contained) and the like. Even if the resin (A) is in a form carrying a structure corresponding to the acid generator, the composition of the present invention may further contain an acid generator (that is, a compound (B) to be described later) which is not supported by the resin (A).

The repeating unit having a structure corresponding to the acid generator may be the following repeating unit, but is not limited thereto.

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In addition to the repeating structural unit, in order to adjust dry etching resistance or standard developer compatibility, substrate adhesion, resist profile, and analysis of general necessary characteristics as a sensitizing ray-sensitive or radiation-sensitive resin composition The resin (A) used in the composition of the present invention may have various repeating structural units, such as force, heat resistance, sensitivity, and the like.

Examples of such a repeating structural unit include repeating structural units corresponding to the following monomers, but are not limited to these repeating structural units.

Thereby, the properties required for the resin used in the composition of the present invention, in particular, the fine adjustment of the following properties, etc. can be achieved: (1) solubility in a coating solvent, and (2) film forming property (glass transition point) ), (3) alkali developability, (4) thin film formation (hydrophobicity, selection of alkali-soluble groups), (5) Adhesiveness of the unexposed part to the substrate, and (6) dry etching resistance.

Examples of such a monomer include those selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. A compound having one addition polymerizable unsaturated bond or the like.

In addition, if it is an addition polymerizable unsaturated compound copolymerizable with the monomer corresponding to the said various repeating structural unit, it can copolymerize.

In the resin (A) used in the composition of the present invention, in order to adjust dry etching resistance or standard developer compatibility, substrate adhesion, resist profile, of the sensitizing ray-sensitive or radiation-sensitive resin composition, Further, as the resolution, heat resistance, sensitivity, and the like of the general required performance of the sensitized ray-sensitive or radiation-sensitive resin composition, the molar ratio of each repeating structural unit is preferably set.

When the composition of the present invention is a composition for ArF exposure, the resin (A) used in the composition of the present invention preferably has substantially no aromatic ring from the viewpoint of transparency of ArF light. In the resin, the ratio of the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and desirably 0 mol%, that is, no aromatic group, The resin (A) is preferably a monocyclic or polycyclic alicyclic hydrocarbon structure.

The form of the resin (A) in the present invention may be any of a random type, a block type, a comb type, and a star type. The resin (A) can be synthesized, for example, by radical polymerization, cationic polymerization, or anionic polymerization of an unsaturated monomer corresponding to each structure. In addition, polymerization is carried out using unsaturated monomers corresponding to the precursors of the respective structures. Thereafter, a polymer reaction is carried out, whereby a target resin can also be obtained.

When the composition of the present invention contains a hydrophobic resin (HR) to be described later, the resin (A) is preferably free from fluorine atoms and germanium atoms from the viewpoint of compatibility with the hydrophobic resin (HR). In the resin, the ratio of the repeating unit containing a fluorine atom or a ruthenium atom is preferably 5 mol% or less, more preferably 3 mol% or less, and desirably 0 mol%.

The resin (A) used in the composition of the present invention is preferably a resin in which all repeating units contain a (meth) acrylate-based repeating unit. In this case, it is possible to use a resin in which all repeating units are methacrylate-based repeating units, all repeating units are acrylate-based repeating units, and all repeating units are composed of methacrylate-based repeating units and acrylate-based repeating units. Any of the resins formed, but preferably the acrylate-based repeating unit is 50 mol% or less of all repeating units.

The resin (A) in the present invention can be synthesized according to a conventional method (for example, a method conventionally used in the field of polymer synthesis such as radical polymerization, living radical polymerization, anionic polymerization, or cationic polymerization). For example, as a general synthesis method, a batch polymerization method in which a monomer species and a starter are dissolved in a solvent and heated to carry out polymerization is used, and the monomer species and the start are carried out for 1 hour to 10 hours. The solution of the agent is added dropwise to a dropping polymerization method or the like in a heating solvent, and preferably a dropping polymerization method. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, or ketones such as methyl ethyl ketone and methyl isobutyl ketone, such as ethyl acetate. An ester solvent, a guanamine solvent such as dimethylformamide or dimethylacetamide, and a group of the present invention dissolved as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or cyclohexanone described later. The solvent of the product. More preferably, the polymerization is carried out using the same solvent as the solvent used in the photosensitive composition of the present invention. Thereby, generation of particles during storage can be suppressed.

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. The polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) as a polymerization initiator. The radical initiator is preferably an azo initiator, and more preferably an azo initiator having an ester group, a cyano group or a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), and the like. The initiator is added in an additional step or in a stepwise manner, and after completion of the reaction, it is introduced into a solvent, and the desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is from 5% by mass to 50% by mass, preferably from 10% by mass to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

After completion of the reaction, the mixture was allowed to cool to room temperature and purified. A general method such as a purification method in a solution state or a purification method in a solid state, and a purification method in a solution state is a liquid solution in which residual monomers or oligomer components are removed by washing with water or by combining an appropriate solvent. Extraction method, extraction and removal of ultrafiltration or the like of a specific molecular weight or less; purification method in a solid state is a method of removing a residual monomer by solidifying a resin in a poor solvent by dropping a resin solution into a poor solvent The reprecipitation method, or washing the filtered resin slurry with a poor solvent, or the like.

For example, the solvent is poorly soluble or insoluble (poor solvent) by a volume of 10 times or less, preferably 10 times to 5 times the volume of the reaction solution. The resin is precipitated as a solid.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent of the polymer, and may correspond to the type of the polymer, from hydrocarbons, halogenated hydrocarbons, A nitro compound, an ether, a ketone, an ester, a carbonate, an alcohol, a carboxylic acid, water, a mixed solvent containing these solvents, and the like are suitably selected and used. Among these, as the precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferred.

The amount of the precipitation or reprecipitation solvent to be used may be appropriately selected in consideration of efficiency, productivity, etc., and is usually 100 parts by mass to 10,000 parts by mass, preferably 200 parts by mass to 2,000 parts by mass, more preferably 100 parts by mass of the polymer solution. It is 300 parts by mass to 1000 parts by mass.

The temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency or workability, but it is usually about 0 ° C to 50 ° C, preferably near room temperature (for example, about 20 ° C to 35 ° C). The precipitation or reprecipitation operation can be carried out by a known method such as a batch type or a continuous type using a conventional mixing container such as a stirring tank.

The precipitated or reprecipitated polymer is usually subjected to conventional solid-liquid separation such as filtration or centrifugation, and dried for use. Filtration using a solvent resistant filter material is preferably carried out under pressure. The drying is carried out under normal pressure or reduced pressure (preferably under reduced pressure) at a temperature of from about 30 ° C to about 100 ° C, preferably from about 30 ° C to about 50 ° C.

Further, the resin may be precipitated and separated once, and then dissolved again in a solvent to be in contact with a solvent in which the resin is poorly soluble or insoluble. That is, it may also include the following steps Method: after the end of the radical polymerization reaction, contacting the polymer with a solvent which is poorly soluble or insoluble, thereby precipitating the resin (step a); separating the resin from the solution (step b); redissolving in the solvent Preparing the resin solution A (step c); thereafter, contacting the resin solution A with the solvent which is poorly soluble or insoluble in the resin is 10 times the volume of the resin solution A (preferably 5 times or less by volume) Thereby, the resin solid is precipitated (step d); the precipitated resin is separated (step e).

In addition, in order to suppress aggregation of the resin after the preparation of the composition, for example, a step of dissolving the synthesized resin in a solvent to form a solution may be added as described in JP-A-2009-037108. The solution is then heated at about 30 ° C to 90 ° C for about 30 minutes to about 4 hours.

It is preferred to reduce unreacted low molecular components (monomers, oligomers) as much as possible by these purification steps.

The weight average molecular weight of the resin (A) in the present invention is preferably from 6,000 to 50,000, more preferably from 8,000 to 30,000, most preferably from 10,000 to 25,000, in terms of polystyrene by the GPC method. By setting it as this molecular weight range, it is expectable that the solubility with respect to an organic type developing solution becomes a suitable value.

The degree of dispersion (molecular weight distribution) is usually 1.0 to 3.0, and a resin having a degree of dispersion (molecular weight distribution) of preferably 1.0 to 2.6, more preferably 1.0 to 2.0, particularly preferably 1.4 to 2.0 is used. The more the resin having a small molecular weight distribution, the more excellent the resolution and the resist shape, and the smoother the side wall of the resist pattern, the more excellent the roughness.

In the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention, the blending ratio of the resin (A) in the entire composition is preferably 30 in the total solid content. The amount is from % to 99% by mass, more preferably from 60% by mass to 95% by mass.

Further, in the present invention, the resin (A) may be used alone or in combination of two or more.

Specific examples of the resin (A) are shown below, but are not limited to these specific examples.

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[A compound which generates an acid by irradiation with actinic rays or radiation]

The composition of the present invention may also contain a compound which generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (B)" or "acid generator").

In one embodiment of the present invention, examples of the acid generator include compounds represented by the following formula (ZI), formula (ZII) or formula (ZIII).

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

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

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

Further, it may be a compound having a plurality of structures represented by the general formula (ZI). For example, it may be a compound having a structure in which at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) and R ₂₀₁ ~ of another compound represented by the general formula (ZI) At least one of R ₂₀₃ has a structure in which a single bond or a linking group is bonded.

Z ^- represents a non-nucleophilic anion (an anion having a significantly lower ability to produce a nucleophilic reaction).

Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkyl group). a carboxylate anion or the like), a sulfonyl quinone imine anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl) methide anion, or the like.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number It is a 3 to 30 cycloalkyl group.

The aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, the cycloalkyl group and the aryl group exemplified above may have a substituent. Specific examples thereof include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably carbon). The number is 3 to 15), the aryl group (preferably having a carbon number of 6 to 14), the alkoxycarbonyl group (preferably having a carbon number of 2 to 7), and the sulfhydryl group (preferably having a carbon number of 2 to 12). , alkoxycarbonyloxy group (preferably having a carbon number of 2 to 7), alkylthio group (preferably having a carbon number of 1 to 15), alkylsulfonyl group (preferably having a carbon number of 1 to 15) An alkylimidosulfonyl group (preferably having a carbon number of 2 to 15), an aryloxysulfonyl group (preferably having a carbon number of 6 to 20), or an alkylaryloxysulfonyl group (preferably) a carbon number of 7 to 20), a cycloalkylaryloxysulfonyl group (preferably having a carbon number of 10 to 20), an alkoxyalkoxy group (preferably having a carbon number of 5 to 20), and a cycloalkane Alkoxy alkoxy group (preferably having a carbon number of 8 to 20) or the like. The aryl group and the ring structure of each group may further have an alkyl group (preferably having a carbon number of 1 to 15) as a substituent.

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthyl group. Butyl and the like.

Examples of the sulfonyl quinone imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)phosphonium anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of the alkyl group include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group, or a cycloalkylaryloxy group. A sulfonyl group or the like is preferably a fluorine atom or an alkyl group substituted by a fluorine atom.

Examples of the other Z ^- may include phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), and cesium fluoride (for example, SbF ₆ ^- ).

As the Z ^- , an aliphatic sulfonate anion having at least the α-position substituted by a fluorine atom of the sulfonic acid, an aromatic sulfonate anion substituted by a fluorine atom or a fluorine atom-containing group, and a double substituted by a fluorine atom of the alkyl group Alkylsulfonyl) anthracene anion, a tris(alkylsulfonyl)methide anion having an alkyl group substituted with a fluorine atom.

In one aspect of the invention, the number of fluorine atoms contained in the anion of Z ^- is preferably 2 or 3.

From the viewpoint of acid strength, in order to enhance the sensitivity, it is preferred that the generated acid has a pKa of -1 or less.

Examples of the organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having a carbon number of 6 to 15), a linear or branched alkyl group (preferably having a carbon number of 1 to 10), and a ring. An alkyl group (preferably having a carbon number of 3 to 15) or the like.

It is preferred that at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an aryl group, and more preferably all three are aryl groups. The aryl group may be a heteroaryl group such as a hydrazine residue or a pyrrole residue, in addition to a phenyl group or a naphthyl group.

The aryl group, the alkyl group, and the cycloalkyl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably a carbon number). 3 to 15), an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group (preferably having a carbon number of 2 to 7), a mercapto group (preferably having a carbon number of 2 to 12), The alkoxycarbonyloxy group (preferably having a carbon number of 2 to 7) or the like is not limited to the substituents.

Further, two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having a carbon number of 1 to 3), -O-, -S-, -CO-, -SO ₂ -, and the like, but are not limited thereto.

A preferred structure when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group is exemplified by paragraph 0046 of the Japanese Patent Laid-Open Publication No. 2004-233661, paragraph 0047, and Japanese Patent Laid-Open No. 2003- The compound exemplified by the formula (I-1) to the formula (I-70) in the specification of the U.S. Patent Application Publication No. 2003/0224288A1, the specification of the U.S. Patent Application Publication No. 2003/0077540A1. The cation structure of the compound exemplified as the formula (IA-1) to the formula (IA-54) and the formula (IB-1) to the formula (IB-24).

A more preferable example of the compound represented by the formula (ZI) is a compound represented by the formula (ZI-3) or the formula (ZI-4) described below. First, the compound represented by the formula (ZI-3) will be described.

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In the above formula (ZI-3), R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group, and R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group. a cycloalkyl group or an aryl group, wherein R ₂ and R ₃ may be bonded to each other to form a ring, and R ₁ and R ₂ may be bonded to each other to form a ring, and R _X and R _y each independently represent an alkyl group, a cycloalkyl group or an alkenyl group. , an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an alkoxycarbonylcycloalkyl group, and R _X and R _y may be bonded to each other to form a ring, and the ring structure may be Containing an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or a guanamine bond.

Z ^- represents a non-nucleophilic anion.

The alkyl group as R ₁ is preferably a linear alkyl group or a branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specifically, a branched alkyl group is mentioned. The alkyl group of R ₁ may have a substituent.

The cycloalkyl group as R ₁ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a sulfur atom in the ring. The cycloalkyl group of R ₁ may have a substituent.

The alkoxy group as R ₁ is preferably an alkoxy group having 1 to 20 carbon atoms. The alkoxy group of R ₁ may have a substituent.

The cycloalkoxy group as R ₁ is preferably a cycloalkyloxy group having 3 to 20 carbon atoms. The cycloalkoxy group of R ₁ may have a substituent.

The aryl group as R ₁ is preferably an aryl group having 6 to 14 carbon atoms. The aryl group of R ₁ may have a substituent.

Examples of the alkenyl group of R ₁ include a vinyl group and an allyl group.

R ₂ and R _{3 each} represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be bonded to each other to form a ring. Here, at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, or an aryl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group for R ₂ and R ₃ are the same as those of the specific examples and preferred examples described for R ₁ . When R ₂ and R ₃ are bonded to each other to form a ring, the total number of carbon atoms which contribute to ring formation contained in R ₂ and R ₃ is preferably 4 to 7, particularly preferably 4 or 5.

R ₁ and R ₂ may be bonded to each other to form a ring. When R ₁ and R ₂ are bonded to each other to form a ring, R ₁ is preferably an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent), and R ₂ is an alkylene group having a carbon number of 1 to 4. (Methylene group or ethyl group is preferred), and a preferred substituent is the same as the substituent which the aryl group as R ₁ may have. In another embodiment in which R ₁ and R ₂ are bonded to each other to form a ring, R ₁ is a vinyl group, and R ₂ is preferably an alkylene group having 1 to 4 carbon atoms.

The alkyl group represented by R _X and R _y is preferably an alkyl group having 1 to 15 carbon atoms.

The cycloalkyl group represented by R _X and R _y is preferably a cycloalkyl group having 3 to 20 carbon atoms.

The alkenyl group represented by R _X and R _y is preferably an alkenyl group having 2 to 30 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

The aryl group represented by R _X and R _y is, for example, an aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

The alkyl moiety and the 2-oxo group an alkoxycarbonyl group by group R _X and R _y is represented by, for example, previously reported as R _X and R _y are exemplified.

As part of 2-oxo-cycloalkyl-cycloalkyl group and an alkoxycarbonyl group by a cycloalkyl group of R _X and R _y is represented by, for example, previously reported as R _X and R _y are exemplified.

Z ^- include, for example, as in the general formula (ZI) Z ^- those recited.

The compound represented by the formula (ZI-3) is preferably a compound represented by the following formula (ZI-3a) and formula (ZI-3b).

In the formula (ZI-3a) and the formula (ZI-3b), R ₁ , R ₂ and R ₃ are as defined in the above formula (ZI-3).

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, preferably an oxygen atom or a nitrogen atom. m, n, p and q represent an integer, preferably 0 to 3, more preferably 1 to 2, and particularly preferably 1. The alkylene group to which S ⁺ and Y are bonded may have a substituent, and as a preferable substituent, an alkyl group may be mentioned.

When Y is a nitrogen atom, R ₅ represents a monovalent organic group, and when Y is an oxygen atom or a sulfur atom, R ₅ is absent. R _{5 is} preferably a group having an electron withdrawing group, and particularly preferably a group represented by the following formula (ZI-3a-1) to formula (ZI-3a-4).

In the above (ZI-3a-1) to (ZI-3a-3), R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and is preferably an alkyl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group of R are the same as those of the specific examples and preferred examples described for R _{1 in} the above formula (ZI-3).

In the above (ZI-3a-1) to (ZI-3a-4), * represents a bond to be bonded to a nitrogen atom of Y in the compound represented by the formula (ZI-3a).

When Y is a nitrogen atom, R _{5 is} particularly preferably a group represented by -SO ₂ -R ₄ . R ₄ represents an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group of R ₄ are the same as those of the specific examples and preferred examples described for R ₁ .

Z ^- include, for example, as in the general formula (ZI) Z ^- those recited.

Specific examples of the cationic moiety of the compound represented by the formula (ZI-3) are listed below.

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Next, the compound represented by the formula (ZI-4) will be described.

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In the formula (ZI-4), R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.

When a plurality of R ₁₄ are present, each independently represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a ring. The base of an alkyl group. These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ groups may be bonded to each other to form a ring, and may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom as an atom constituting the ring. These groups may have a substituent.

1 represents an integer from 0 to 2.

r represents an integer from 0 to 8.

Z ^- represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^- in the general formula (ZI).

In the formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched, and preferably has 1 to 10 carbon atoms.

Examples of the cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.

The alkoxy group of R ₁₃ and R ₁₄ is linear or branched, and preferably has 1 to 10 carbon atoms.

The alkoxycarbonyl group of R ₁₃ and R ₁₄ is linear or branched, and preferably has 2 to 11 carbon atoms.

Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

Specific examples of the alkyl group of the alkylcarbonyl group of R ₁₄ include the same examples as the alkyl group of the above R ₁₃ to R ₁₅ .

The alkylsulfonyl group and the cycloalkylsulfonyl group of R ₁₄ are linear, branched or cyclic, and preferably have 1 to 10 carbon atoms.

Examples of the substituent which the respective groups may have include a halogen atom (e.g., a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxy group. A carbonyloxy group or the like.

The ring structure 2 R ₁₅ may be bonded to each other to form include 2 R ₁₅ in the general formula 5 or 6 together form a (ZI-4) sulfur atom in the ring, particularly preferably of 5 The ring (i.e., the tetrahydrothiophene ring or the 2,5-dihydrothiophene ring) may also be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent, and examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, and an alkoxycarbonyl group. , alkoxycarbonyloxy and the like. There may be a plurality of substituents for the ring structure, and in addition, the groups may be bonded to each other to form a ring.

R ₁₅ in the formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, and a divalent group in which two R ₁₅ are bonded to each other and form a tetrahydrothiophene ring structure together with a sulfur atom. Particularly preferably, two R ₁₅ are bonded to each other and together with a sulfur atom form a divalent group of a tetrahydrothiophene ring structure.

The substituent which R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, or an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

As 1, it is preferably 0 or 1, more preferably 1.

As r, it is preferably 0 to 2.

Specific examples of the cationic structure of the compound represented by the formula (ZI-3) or the formula (ZI-4) described above, in addition to the above-mentioned Japanese Patent Laid-Open No. 2004-233661, Japanese Patent No. In addition to the cationic structure of the compound and the like exemplified in the specification of the U.S. Patent Application Publication No. 2003/0224288 A1, and the specification of the U.S. Patent Application Publication No. 2003/0077540 A1, for example, Japanese Patent Laid-Open No. 2011-53360 The cationic structure in the chemical structure and the like exemplified in paragraph 0046, paragraph 0047, paragraph 0072 to paragraph 0077, paragraph 0107 to paragraph 0110 of the gazette, paragraph 0135 to paragraph 0137, paragraph 0151 of Japanese Patent Laid-Open No. 2011-53430 The cationic structure or the like in the chemical structure or the like exemplified in paragraphs 0196 to 0199.

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

The aryl group, the alkyl group or the cycloalkyl group as R ₂₀₄ to R _{207 is the same} as the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI).

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. The substituent may be a substituent which the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI) may have.

Z ^- include, for example, as in the general formula (ZI) Z ^- those recited.

Next, a preferred structure of the non-nucleophilic anion Z ^- will be described.

The non-nucleophilic anion Z ^{- is} preferably a sulfonate anion represented by the formula (2).

Xf in the formula (2) independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ₇ and R ₈ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₇ and R ₈ are present, they may be the same or different.

L represents a divalent linking group, and when there are a plurality of L, they may be the same or different.

A represents an organic group having a cyclic structure.

x represents an integer from 1 to 20. y represents an integer from 0 to 10. z represents an integer from 0 to 10.

The anion of the formula (2) will be described in more detail.

As described above, Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom, and the alkyl group in the alkyl group substituted by a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

As Xf, a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferable. Specifically, a fluorine atom or CF _{3 is} preferred. Particularly preferably, both Xf are fluorine atoms.

R ₇ and R _{8 each} represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom, and the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. More preferably, it is a perfluoroalkyl group having a carbon number of 1 to 4. Specific examples of the alkyl group substituted with at least one fluorine atom of R ₇ and R ₈ are preferably CF ₃ .

L represents a divalent linking group, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, -N(Ri)- (wherein Ri Represents a hydrogen atom or an alkyl group, an alkyl group (preferably having a carbon number of 1 to 6), a cycloalkyl group (preferably having a carbon number of 3 to 10), and an alkenyl group (preferably having a carbon number of 2) ~6) or a combination of a plurality of such divalent linking groups, etc., preferably -COO-, -OCO-, -CO-, -SO ₂ -, -CON(Ri)-, -SO ₂ N(Ri)-, -CON(Ri)-alkylene-, -N(Ri)CO-alkylene-, -COO-alkylene- or -OCO-alkylene-, more preferably - COO-, -OCO-, -SO ₂ -, -CON(Ri)- or -SO ₂ N(Ri)-. L may be the same or different when there are a plurality of times.

The alkyl group as Ri is preferably a linear alkyl group or a branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specifically, a linear alkyl group and a branched alkyl group are mentioned. Examples of the alkyl group having a substituent include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group.

The organic group having a cyclic structure of A is not particularly limited as long as it contains a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (not only In the case of containing aromatics, it also includes those which do not have aromaticity, and for example, a tetrahydropyran ring structure or a lactone ring structure.

As the alicyclic group, it may be a single ring or a polycyclic ring. Further, an alicyclic group containing a nitrogen atom such as a piperidinyl group, a decahydroquinolyl group or a decahydroisoquinolyl group is also preferred. Among them, from the viewpoint of suppressing the diffusibility in the film in the PEB (post-exposure heating) step and improving the exposure latitude, it is preferably a norbornyl group, a tricyclodecyl group, a tetracyclodecyl group, or a tetracyclic ten. An alicyclic group having a bulky structure having a carbon number of 7 or more, such as a dialkyl group, an adamantyl group, a decahydroquinolyl group or a decahydroisoquinolyl group.

Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Among them, from the viewpoint of absorbance at 193 nm, naphthalene having low absorbance is preferred.

Examples of the heterocyclic group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, a furan ring, a thiophene ring, and a pyridine ring are preferred.

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched, or cyclic, preferably having a carbon number of 1 to 12) and an aryl group ( Preferably, the carbon number is 6 to 14), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, a urethane group, a urea group, a thioether group, a sulfonylamino group, a sulfonate group, a cyano group. Wait.

Further, carbon constituting the organic group having a cyclic structure (carbon which contributes to ring formation) may be a carbonyl carbon.

x is preferably from 1 to 8, more preferably from 1 to 4, and particularly preferably 1. y is preferably 0 to 4, more preferably 0 or 1, and still more preferably 0. z is preferably 0 to 8, more preferably 0 to 4, and still more preferably 1.

Moreover, in one aspect of the invention, it is preferred that the number of fluorine atoms contained in the anion represented by the formula (2) is 2 or 3. Thereby, the effect of the present invention can be further improved.

Specific examples of the sulfonate anion structure represented by the general formula (2) are listed below, but the present invention is not limited to these specific examples.

As Z ^- , a sulfonate anion represented by the following formula (B-1) is also preferable.

In the above formula (B-1), R _b1 each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF ₃ ).

n represents an integer from 0 to 4.

n is preferably an integer of 0 to 3, more preferably 0 or 1.

X _b1 represents a single bond, an alkylene group, an ether bond, an ester bond (-OCO- or -COO-), a sulfonate bond (-OSO ₂ - or -SO ₃ -), or a combination thereof.

X _{b1 is} preferably an ester bond (-OCO- or -COO-) or a sulfonate bond (-OSO ₂ - or -SO ₃ -), more preferably an ester bond (-OCO- or -COO-).

R _b2 represents an organic group having 6 or more carbon atoms.

The organic group having 6 or more carbon atoms in R _b2 is preferably a large-volume group, and examples thereof include an alkyl group having 6 or more carbon atoms, an alicyclic group, an aryl group, and a heterocyclic group.

The alkyl group having 6 or more carbon atoms in R _b2 may be linear or branched, and is preferably a linear or branched alkyl group having 6 to 20 carbon atoms, and examples thereof include a linear chain. Hexyl or branched hexyl, linear heptyl or branched heptyl, linear octyl or branched octyl, and the like. From the viewpoint of the size, a branched alkyl group is preferred.

The alicyclic group having 6 or more carbon atoms in R _b2 may be a monocyclic ring or a polycyclic ring. Among them, from the viewpoint of suppressing the diffusibility in the film in the PEB (post-exposure heating) step and improving the Mask Error Enhancement Factor (MEEF), it is preferably a norbornyl group or a tricyclodecyl group. An alicyclic group having a bulky structure having a carbon number of 7 or more, such as tetracyclodecylalkyl, tetracyclododecyl, or adamantyl.

The aryl group having 6 or more carbon atoms of R _b2 may be a monocyclic ring or a polycyclic ring. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthracenyl group. Among them, a naphthyl group having a relatively low absorbance at 193 nm is preferred.

The heterocyclic group having 6 or more carbon atoms of R _b2 may be a monocyclic ring or a polycyclic ring, but the polycyclic ring may further inhibit the diffusion of an acid. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the aromatic heterocyclic ring include a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, and a dibenzothiophene ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

The substituent having 6 or more carbon atoms of R _b2 may further have a substituent. Examples of the further substituent include an alkyl group (which may be either a straight chain or a branched group, preferably a carbon number of 1 to 12) or a cycloalkyl group (which may be monocyclic, polycyclic or spiro). Any one preferably has a carbon number of 3 to 20), an aryl group (preferably having a carbon number of 6 to 14), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, a urethane group, or a ureido group. , thioether group, sulfonamide group, and sulfonate group. Further, the carbon constituting the alicyclic group, the aryl group or the heterocyclic group (carbon which contributes to ring formation) may be a carbonyl carbon.

Specific examples of the sulfonate anion structure represented by the general formula (B-1) are listed below, but the present invention is not limited to these specific examples. Further, in the following specific examples, the sulfonate anion corresponding to the above formula (2) is also included.

As Z ^- , a sulfonate anion represented by the following formula (AI) is also preferable.

In the formula (AI), R ₁ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group or a heteroaryl group.

R ₂ is a divalent linking group.

Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom.

n ₁ and n ₂ are each independently 0 or 1.

The alkyl group represented by the above R ₁ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferred is an alkyl group having 1 to 4 carbon atoms.

Further, the alkyl group may have a substituent (preferably a fluorine atom), and the alkyl group having a substituent is preferably an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine atom, more preferably A perfluoroalkyl group having a carbon number of 1 to 5.

The alkyl group represented by the above R ₁ is preferably a methyl group, an ethyl group or a trifluoromethyl group, more preferably a methyl group or an ethyl group.

The monovalent alicyclic hydrocarbon group represented by the above R ₁ preferably has a carbon number of 5 or more. Further, the monovalent alicyclic hydrocarbon group preferably has a carbon number of 20 or less, more preferably a carbon number of 15 or less. The monovalent alicyclic hydrocarbon group may be a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group. A part of -CH ₂ - of the alicyclic hydrocarbon group may be substituted by -O- or -C(=O)-.

The monocyclic alicyclic hydrocarbon group is preferably a carbon number of 5 to 12, preferably a cyclopentyl group, a cyclohexyl group or a cyclooctyl group.

The polycyclic alicyclic hydrocarbon group is preferably a carbon number of 10 to 20, preferably a norbornyl group, an adamantyl group or a noradamantyl group.

The aryl group represented by the above R ₁ preferably has a carbon number of 6 or more. Further, the aryl group preferably has a carbon number of 20 or less, more preferably a carbon number of 15 or less.

The heteroaryl group represented by the above R ₁ preferably has a carbon number of 2 or more. Further, the heteroaryl group preferably has a carbon number of 20 or less, more preferably a carbon number of 15 or less.

The aryl group and the heteroaryl group may be a monocyclic aryl group or a monocyclic heteroaryl group, or may be a polycyclic aryl group or a polycyclic heteroaryl group.

Examples of the monocyclic aryl group include a phenyl group and the like.

Examples of the polycyclic aryl group include a naphthyl group and an anthracenyl group.

Examples of the monocyclic heteroaryl group include a pyridyl group, a thienyl group, a furyl group and the like.

Examples of the polycyclic heteroaryl group include a quinolyl group and an isoquinolyl group.

The monovalent alicyclic hydrocarbon group, aryl group, and heteroaryl group of the above R ₁ may further have a substituent. Examples of such a further substituent include a hydroxyl group and a halogen atom (a fluorine atom, a chlorine atom, and a bromine group). Atom, an iodine atom, etc.), a nitro group, a cyano group, a decylamino group, a sulfonylamino group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, a decyloxy group, or a carboxyl group.

R _{1 is} particularly preferably a cyclohexyl group or an adamantyl group.

The divalent linking group represented by the above R ₂ is not particularly limited, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, and -SO _{2 .} - an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having a carbon number of 3 to 30), an alkenyl group (preferably carbon) a number of 2 to 30 alkenyl groups, an aryl group (preferably a carbon number of 6 to 30 aryl groups), a heteroaryl group (preferably a carbon number of 2 to 30 heteroaryl groups) And a combination of two or more of these. The alkylene group, the cycloalkylene group, the alkenyl group, the aryl group and the heteroaryl group may further have a substituent, and a specific example of such a substituent is a monovalent alicyclic hydrocarbon group as R ₁ . The aryl group and the heteroaryl group may have the same substituents as described above.

The divalent linking group represented by the R ₂ is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heteroaryl group, more preferably an alkyl group, and further preferably It is an alkylene group having a carbon number of 1 to 10, and particularly preferably an alkylene group having a carbon number of 1 to 5.

Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 4 carbon atoms. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

Rf is preferably a fluorine atom or a perfluoroalkyl group having a carbon number of 1 to 4. More specifically, Rf is preferably a fluorine atom or CF ₃ .

n _{1 is} preferably 1.

n _{2 is} preferably 1.

Preferred specific examples of the sulfonate anion represented by the above formula (A-I) are listed below, but the present invention is not limited to these specific examples. Further, in the following specific examples, the sulfonate anion corresponding to the above formula (2) is also included.

[化94]

The non-nucleophilic anion Z ^- may also be a disulfonyl sulfinyl anion represented by the formula (2').

[化95]

In the formula (2'), Xf is as defined in the above formula (2), and preferred examples are also the same. In the general formula (2'), two Xf may be bonded to each other to form a ring structure.

As the disulfonyl quinoid anion of Z ^- , a bis(alkylsulfonyl) quinone imine is preferred.

The alkyl group in the bis(alkylsulfonyl) quinone imine anion is preferably an alkyl group having 1 to 5 carbon atoms.

The two alkyl groups in the bis(alkylsulfonyl) quinone imine anion may be bonded to each other to form an alkylene group (preferably having a carbon number of 2 to 4), and an oxime imine group and two sulfonyl groups. Together form a ring. The ring structure which can be formed as an bis(alkylsulfonyl) quinone imine anion is preferably a 5-membered ring to a 7-membered ring, more preferably a 6-membered ring.

Examples of the substituent which the alkyl group and the two alkyl groups are bonded to each other may be a halogen atom, an alkyl group substituted by a halogen atom, an alkoxy group, an alkylthio group or an alkoxysulfonate. The group, the aryloxysulfonyl group, the cycloalkylaryloxysulfonyl group and the like are preferably a fluorine atom or an alkyl group substituted by a fluorine atom.

Further, examples of the acid generator include compounds represented by the following formula (ZV).

[化96]

In the formula (ZV), R ₂₀₈ represents an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the aryl group of R ₂₀₈ include the same as the specific examples of the aryl group of R ₂₀₁ to R ₂₀₃ in the above formula (ZI).

Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ are the same as the specific examples of the alkyl group and the cycloalkyl group as R ₂₀₁ to R ₂₀₃ in the above formula (ZI).

Examples of the alkylene group of A include an alkylene group having a carbon number of 1 to 12 (for example, a methylene group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, etc.). The alkenyl group of A may, for example, be an alkenyl group having 2 to 12 carbon atoms (e.g., a vinyl group, a propenyl group, a butenyl group, etc.), and as the aryl group of A, a carbon number of 6 to 10 may be mentioned. Aryl group (for example, phenyl, methylphenyl, naphthyl, etc.).

Examples of the acid generator are listed below. However, the invention is not limited to the examples.

[化97]

[化98]

[化99]

[化100]

The acid generator may be used alone or in combination of two or more.

The content of the acid generator in the composition is preferably from 0.1% by mass to 30% by mass, more preferably from 1% by mass to 28% by mass, even more preferably 3% by mass based on the total solid content of the composition. 25 mass%.

[hydrophobic resin]

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may contain a hydrophobic resin (hereinafter, also referred to as "hydrophobic resin (HR)" or simply "resin (HR), particularly when applied to liquid immersion exposure. )"). Further, the hydrophobic resin (HR) is preferably different from the resin (A).

Thereby, the hydrophobic resin (HR) is biased to exist on the surface layer of the film, and when the liquid immersion medium is water, the static/dynamic contact angle of the surface of the resist film with respect to water can be enhanced, and the liquid immersion liquid followability can be improved. Further, when the pattern formation of the present invention is carried out by EUV exposure, it is also expected to apply a hydrophobic resin (HR) by suppressing so-called outgas.

The hydrophobic resin (HR) is preferably designed to be present at the interface as described above, but unlike the surfactant, it is not necessarily required to have a hydrophilic group in the molecule, and it does not contribute to uniformity of the polar substance/nonpolar substance. Mix ground.

The hydrophobic resin (HR) is preferably one having a "fluorine atom", a "deuterium atom", and a "CH ₃ partial structure contained in a side chain portion of the resin" from the viewpoint of being present on the surface layer of the film. More preferably, it is more than 2 types.

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

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

The alkyl group having a fluorine atom (preferably having a carbon number of 1 to 10, more preferably 1 to 4 carbon atoms) is a linear alkyl group or a branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and further may be further It has a substituent other than a fluorine atom.

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

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

The alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom, and the aryl group containing a fluorine atom are preferably a group represented by the following formula (F2) to formula (F4), but The invention is not limited to this.

[化104]

In the general formulae (F2) to (F4), R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched). Wherein at least one of R ₅₇ to R ₆₁ , at least one of R ₆₂ to R ₆₄ , and at least one of R ₆₅ to R ₆₈ each independently represent a fluorine atom or an alkane having at least one hydrogen atom substituted with a fluorine atom. Base (preferably having a carbon number of 1 to 4).

Preferably, R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are each a fluorine atom. R ₆₂ , R ₆₃ and R _{68 are} preferably an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom (preferably having a carbon number of 1 to 4), more preferably a perfluoroalkyl group having a carbon number of 1 to 4. R ₆₂ and R ₆₃ may be bonded to each other to form a ring.

Specific examples of the group represented by the formula (F2) include p-fluorophenyl group, pentafluorophenyl group, and 3,5-bis(trifluoromethyl)phenyl group.

Specific examples of the group represented by the formula (F3) include a trifluoromethyl group, a pentafluoropropyl group, a pentafluoroethyl group, a heptafluorobutyl group, a hexafluoroisopropyl group, and a heptafluoroisopropyl group. Hexafluoro(2-methyl)isopropyl, nonafluorobutyl, octafluoroisobutyl, nonafluorohexyl, nonafluoro-tert-butyl, perfluoroisopentyl, perfluorooctyl, perfluoro(three Methyl)hexyl, 2,2,3,3-tetrafluorocyclobutyl, perfluorocyclohexyl, and the like. Preferred is hexafluoroisopropyl, heptafluoroisopropyl, Hexafluoro(2-methyl)isopropyl, octafluoroisobutyl, nonafluoro-tert-butyl, perfluoroisopentyl, more preferably hexafluoroisopropyl or heptafluoroisopropyl.

Specific examples of the group represented by the formula (F4) include -C(CF ₃ ) ₂ OH, -C(C ₂ F ₅ ) ₂ OH, -C(CF ₃ )(CH ₃ )OH, -CH(CF ₃ )OH or the like, preferably -C(CF ₃ ) ₂ OH.

The partial structure containing a fluorine atom may be directly bonded to the main chain, and further, may be selected from an alkyl group, a phenyl group, an ether bond, a thioether bond, a carbonyl group, an ester bond, a guanamine bond, or an amide group. A group in a group consisting of an ester bond and a urea-based bond, or a combination of two or more of these groups, is bonded to the main chain.

Specific examples of the repeating unit containing a fluorine atom are shown below, but the present invention is not limited thereto.

In a specific example, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ . X ₂ represents -F or -CF ₃ .

[化105]

[化106]

The hydrophobic resin (HR) may also contain a ruthenium atom. It is preferably a resin having an alkyl fluorenyl group structure (preferably a trialkyl decyl group) or a cyclic siloxane structure as a partial structure containing a ruthenium atom.

Specific examples of the alkyl fluorenyl group structure and the cyclic oxirane structure include a group represented by the following formula (CS-1) to formula (CS-3).

In the general formula (CS-1) to the general formula (CS-3), R ₁₂ to R ₂₆ each independently represent a linear alkyl group or a branched alkyl group (preferably having a carbon number of 1 to 20) or a cycloalkyl group. (It is preferred that the carbon number is 3 to 20).

L ₃ to L ₅ represent a single bond or a divalent linking group. Examples of the divalent linking group include a group selected from an alkyl group, a phenyl group, an ether bond, a thioether bond, a carbonyl group, an ester bond, a guanamine bond, a urethane bond, or a urea bond. One type or a combination of two or more types (preferably, the total carbon number is 12 or less).

n represents an integer from 1 to 5. n is preferably an integer of 2 to 4.

Specific examples of the repeating unit having a group represented by the general formula (CS-1) to the general formula (CS-3) are listed below, but the present invention is not limited thereto. Further, in a specific example, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ .

[化108]

Further, as described above, it is also preferred that the hydrophobic resin (HR) has a CH ₃ moiety structure in the side chain portion.

Here, the partial structure CH ₃ side chain moiety to the resin (HR) is contained (hereinafter, also referred to as "partial structure a side chain CH _3") CH included ethyl, propyl and the like contained in the ₃ Part of the structure.

On the other hand, a methyl group directly bonded to the main chain of the resin (HR) (for example, an α-methyl group having a repeating unit of a methacrylic acid structure) causes a bias toward the resin (HR) due to the influence of the main chain. Since the contribution to the surface is small, it is set to be not included in the CH ₃ partial structure in the present invention.

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

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

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

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

Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkane. The amino group carbonyl group, the arylamino group carbonyl group and the like may further have a substituent.

The hydrophobic resin (HR) is preferably a resin having a repeating unit having a CH ₃ partial structure in a side chain portion, more preferably having a repeating unit represented by the following formula (II), and having the following formula ( At least one of the repeating units (x) represented by V) is such a repeating unit.

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

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

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

X _{b1 is} preferably a hydrogen atom or a methyl group.

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

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

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

The alkyl group having one or more CH ₃ partial structures in R ₂ is preferably a branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group having one or more CH ₃ partial structures in R ₂ may be a monocyclic ring or a polycyclic ring. Specifically, a group having a single ring structure, a bicyclic structure, a tricyclic structure, a tetracyclic structure or the like having a carbon number of 5 or more is exemplified. The carbon number is preferably from 6 to 30, and the carbon number is preferably from 7 to 25. Preferred are norbornyl, cyclopentyl or cyclohexyl.

The alkenyl group having one or more CH ₃ partial structures in R ₂ is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, more preferably a branched alkenyl group.

The aryl group having one or more CH ₃ partial structures in R ₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferred.

The aralkyl group having one or more CH ₃ partial structures in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

As the hydrocarbon group having two or more CH ₃ partial structures in R ₂ , specifically, isobutyl, tert-butyl, 2-methyl-3-butyl, 2,3-dimethyl-2-butyl , 2-methyl-3-pentyl, 3-methyl-4-hexyl, 3,5-dimethyl-4-pentyl, 2,4,4-trimethylpentyl, 2-ethylhexyl , 2,6-dimethylheptyl, 1,5-dimethyl-3-heptyl, 2,3,5,7-tetramethyl-4-heptyl, 3,5-dimethylcyclohexyl 3,5-di-t-butylcyclohexyl, 4-isopropylcyclohexyl, 4-tert-butylcyclohexyl, isobornyl.

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

[111]

The repeating unit represented by the general formula (II) is preferably a (non-acid-decomposable) repeating unit which is stable to an acid, and specifically, preferably does not have a decomposition due to an action of an acid and generates a polar group. The repeating unit of the base.

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

[化112]

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

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

X _{b2 is} preferably a hydrogen atom.

R ₃ is an organic group which is stable to an acid, and more specifically, it is preferably organic having no "base which decomposes due to the action of an acid and generates a polar group" as described in the resin (A). base.

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

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

The alkyl group having one or more CH ₃ partial structures in R ₃ is preferably a branched alkyl group having 3 to 20 carbon atoms.

As the alkyl group having two or more CH ₃ partial structures in R ₃ , specifically, isopropyl, tert-butyl, 2-methyl-3-butyl, 2-methyl-3-pentyl, 3 -methyl-4-hexyl, 3,5-dimethyl-4-pentyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1 , 5-dimethyl-3-heptyl, 2,3,5,7-tetramethyl-4-heptyl, 2,6-dimethylheptyl.

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 the general formula (V) are listed below. Furthermore, the present invention is not limited to this.

The repeating unit represented by the general formula (V) is preferably a stable (non-acid-decomposable) repeating unit for an acid, and specifically, it is preferably not decomposed by an action of an acid and generates a polar group. The repeating unit of the base.

When the resin (HR) contains a CH ₃ moiety structure in the side chain moiety, and further, especially when there is no fluorine atom and a ruthenium atom, the repeat represented by the general formula (II) with respect to all the repeating units of the resin (HR) The content of at least one of the unit and the repeating unit represented by the formula (V) is preferably 90 mol% or more, more preferably 95 mol% or more. The content is usually 100 mol% or less with respect to all the repeating units of the resin (HR).

The resin (HR) contains 90 mol% or more of the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (V) by all the repeating units with respect to the resin (HR) The surface free energy of the resin (HR) is increased by at least one repeating unit (x). As a result, it is difficult for the resin (HR) to be biased toward the surface of the resist film, and the static/dynamic contact angle of the resist film with respect to water can be surely improved, and the liquid immersion liquid followability can be improved.

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

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

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamino group, a sulfonyl fluorenylene group, and an alkylsulfonyl group. Carbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)indenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indenylene, bis(alkylsulfonate) Methyl, bis(alkylsulfonyl) fluorenylene, tris(alkylcarbonyl)methylene, tris(alkylsulfonyl)methylene, and the like.

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

Examples of the repeating unit having an acid group (x) include a repeating unit in which an acid group is directly bonded to a main chain of the resin, such as a repeating unit formed of acrylic acid or methacrylic acid, or a resin via a linking group. Repeating unit with an acid group bonded to the main chain Alternatively, it may be introduced into the terminal of the polymer chain by using a polymerization initiator or a chain transfer agent having an acid group at the time of polymerization, and it is preferred in either case. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a germanium atom.

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

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

[化114]

[化115]

As the group having a lactone structure, an acid anhydride group, or a quinone imine group (y), a group having a lactone structure is particularly preferred.

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

The repeating unit having a group having a lactone structure may, for example, be the same as the repeating unit having a lactone structure described in the section on the acid-decomposable resin (A).

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

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

The hydrophobic resin (HR) may further contain a repeating unit represented by the following formula (VI).

In the formula (VI), R _c31 represents a hydrogen atom, an alkyl group (which may be substituted by a fluorine atom or the like), a cyano group or a -CH ₂ -O-Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. R _{c31 is} preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted by a group containing a fluorine atom or a halogen atom.

L _c3 represents a single bond or a divalent linking group.

The alkyl group of R _c32 in the formula (VI) is preferably a linear alkyl group or a branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 20.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these groups may have a substituent.

R _{c32 is} preferably an unsubstituted alkyl group or an alkyl group substituted by a fluorine atom.

The divalent linking group of L _c3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an ether bond, a phenyl group, and an ester bond (a group represented by -COO-).

The content of the repeating unit represented by the general formula (VI) is preferably from 1 mol% to 100 mol%, more preferably from 10 mol% to 90 mol%, based on all the repeating units in the hydrophobic resin. More preferably, it is 30% by mole to 70% by mole.

It is also preferred that the hydrophobic resin (HR) further contains a repeating unit represented by the following formula (CII-AB).

In the formula (CII-AB), R _c11 ' and R _c12 ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Zc' represents an atomic group containing a bonded carbon atom (C-C) and used to form an alicyclic structure.

The content of the repeating unit represented by the general formula (CII-AB) is preferably from 1 mol% to 100 mol%, more preferably from 10 mol% to 90 mol, based on all the repeating units in the hydrophobic resin. Ear %, and more preferably 30 mole % to 70 mole %.

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

When the hydrophobic resin (HR) contains a fluorine atom, it is relative to the hydrophobic resin. The weight average molecular weight of (HR) and the content of fluorine atoms are preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 80% by mass. Further, among all the repeating units contained in the hydrophobic resin (HR), the repeating unit containing a fluorine atom is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%.

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

On the other hand, especially when the resin (HR) contains a CH ₃ moiety structure in the side chain portion, the resin (HR) is preferably substantially free of fluorine atoms and germanium atoms, and in this case, specifically, relative The content of the repeating unit containing a fluorine atom or a ruthenium atom in all the repeating units in the resin (HR) is preferably 5 mol% or less, more preferably 3 mol% or less, and still more preferably 1 mol% or less. It is desirable to have 0% by mole, that is, no fluorine atom or germanium atom. Further, the resin (HR) preferably contains substantially only a repeating unit containing only an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom. More specifically, in all the repeating units of the resin (HR), the repeating unit containing only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is preferably 95 mol% or more. Preferably, it is 97% or more, more preferably 99% by mole or more, and most preferably 100% by mole.

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

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

The content of the hydrophobic resin (HR) in the composition is preferably from 0.01% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, based on the total solid content of the composition of the present invention, and further preferably It is 0.1% by mass to 7% by mass.

The hydrophobic resin (HR) is the same as the resin (A), and of course, impurities such as metal are small, and the residual monomer or oligomer component is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass. Further, it is more preferably 0.05% by mass to 1% by mass. Thereby, a sensitized ray-sensitive or radiation-sensitive resin composition which does not have a foreign matter in the liquid or does not have a change in sensitivity or the like with time can be obtained. Further, the molecular weight distribution (Mw/Mn, also referred to as dispersion degree) is preferably in the range of 1 to 5 from the viewpoints of the resolution, the resist shape, the side wall of the resist pattern, the roughness, and the like. It is 1 to 3, and more preferably 1 to 2.

The hydrophobic resin (HR) can also be synthesized by various commercial products or by a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which a monomer species and a starter are dissolved in a solvent and heated to carry out polymerization is used, and the monomer species and the start are carried out for 1 hour to 10 hours. The solution of the agent is added dropwise to a dropping polymerization method or the like in a heating solvent, and preferably a dropping polymerization method.

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

Specific examples of the hydrophobic resin (HR) are shown below. Moreover, the molar ratio (corresponding to each repeating unit from the left side), the weight average molecular weight, and the dispersion degree of the repeating unit in each resin are shown in the following table.

[化120]

[化121]

[化123]

[化124]

[化125]

[alkaline compound]

The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce the change in performance caused by the passage of time from exposure to heating. The basic compound which can be used is not particularly limited, and for example, compounds classified into the following (1) to (6) can be used.

(1) Basic compound (N)

The basic compound is preferably a compound (N) having a structure represented by the following formula (A) to formula (E).

[化126]

In the general formula (A) and the general formula (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), or a cycloalkyl group ( Preferably, the carbon number is 3 to 20) or the aryl group (carbon number is 6 to 20), and here, R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

With respect to the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyano group having 1 to 20 carbon atoms. alkyl.

The alkyl groups in the general formula (A) and the general formula (E) are more preferably unsubstituted.

Preferred examples of the compound (N) include anthracene, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like as a more preferable compound ( N), a compound (N) having an imidazole structure, a diazabicyclo structure, a ruthenium hydroxide structure, a ruthenium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, having a hydroxyl group and/or an ether bond An alkylamine derivative, an aniline derivative having a hydroxyl group and/or an ether bond, or the like.

Examples of the compound (N) having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. As the compound (N) having a diazabicyclo structure, 1,4-diazabicyclo[2.2.2]octane, 1,5- Diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, and the like. Examples of the compound (N) having a ruthenium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, benzamidine methylhydrazine hydroxide, and cesium hydroxide containing a 2-oxoalkyl group. Listed triphenylphosphonium hydroxide, tris(t-butylphenyl)phosphonium hydroxide, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methylthiophene hydroxide, 2-oxo hydroxide Propylthiophene and the like. The compound (N) having a ruthenium carboxylate salt structure is one in which the anion portion of the compound (N) having a ruthenium hydroxide structure is a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkane. Carboxylic acid salt and the like. Examples of the compound (N) having a trialkylamine structure include tri(n-butyl)amine and tris(n-octyl)amine. Examples of the aniline compound (N) include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Further preferred examples of the basic compound (N) include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group. . Examples of such a compound include the compound (C1-1) to the compound (C3-3) exemplified in paragraph [0066] of the specification of the U.S. Patent Application Publication No. 2007/0224539 A1.

Further, the following compound is also preferable as the basic compound (N).

[化127]

As the basic compound (N), in addition to the above-mentioned compound, JP-A-2011-22560 [0180] to [0225], and JP-A-2012-137735 (0218) to [0219] can be used. The compound or the like described in the International Publication No. WO2011/158687A1 [0416] to [0438]. The basic compound (N) may also be a basic compound or an ammonium salt compound which causes a decrease in alkalinity by irradiation with actinic rays or radiation.

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

The composition of the present invention may contain a basic compound (N) or may not contain a basic compound (N). When the basic compound (N) is contained, the solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition is The content of the basic compound (N) is usually 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass.

The ratio of use of the acid generator to the basic compound (N) in the composition is preferably an acid generator/basic compound (mole ratio) = 2.5 to 300. In other words, from the viewpoint of sensitivity and resolution, it is preferable that the molar amount is 2.5 or more, and the viewpoint that the resolution of the resist pattern up to the time after the post-exposure heat treatment is reduced becomes thicker. Moer is better than 300 or less. The acid generator/basic compound (N) (mole ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

(2) a basic compound or an ammonium salt compound (F) which causes a decrease in alkalinity by irradiation with actinic rays or radiation

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound or an ammonium salt compound which causes a decrease in alkalinity by irradiation with actinic rays or radiation (hereinafter, also referred to as "compound ( F)").

The compound (F) is preferably a compound (F-1) having a basic functional group or an ammonium group and a group which generates an acidic functional group by irradiation with actinic rays or radiation. That is, the compound (F) is preferably a basic compound having a basic functional group and a group which generates an acidic functional group by irradiation with actinic rays or radiation, or an ammonium group and irradiation with actinic rays or radiation. An ammonium salt compound which produces a group of an acidic functional group.

The compound having a reduced basicity due to decomposition of the compound (F) or the compound (F-1) by irradiation with actinic rays or radiation may be exemplified by the following formula (PA-I) and formula (PA-). II) or a compound represented by the formula (PA-III), in terms of high-level compatibility with LWR, local pattern size uniformity, and Depth Of Field (DOF) Particularly preferred is a compound represented by the formula (PA-II) or the formula (PA-III).

First, the compound represented by the formula (PA-I) will be described.

QA ₁ -(X) _n -BR (PA-I)

In the formula (PA-I), A ₁ represents a single bond or a divalent linking group.

Q represents -SO ₃ H, or -CO ₂ H. Q corresponds to an acidic functional group produced by irradiation with actinic rays or radiation.

X represents -SO ₂ - or -CO-.

n represents 0 or 1.

B represents a single bond, an oxygen atom or -N(Rx)-.

Rx represents a hydrogen atom or a monovalent organic group.

R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.

Next, the compound represented by the formula (PA-II) will be described.

Q ₁ -X ₁ -NH-X ₂ -Q ₂ (PA-II)

In the formula (PA-II), Q ₁ and Q ₂ each independently represent a monovalent organic group. Among them, any of Q ₁ and Q ₂ has a basic functional group. Q ₁ and Q ₂ may be bonded to form a ring, and the ring formed has a basic functional group.

X ₁ and X ₂ each independently represent -CO- or -SO ₂ -.

Further, -NH- corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Next, the compound represented by the formula (PA-III) will be described.

Q ₁ -X ₁ -NH-X ₂ -A ₂ -(X ₃ ) _m -BQ ₃ (PA-III)

In the formula (PA-III), Q ₁ and Q ₃ each independently represent a monovalent organic group. Among them, any of Q ₁ and Q ₃ has a basic functional group. Q ₁ and Q ₃ may be bonded to form a ring, and the ring formed has a basic functional group.

X ₁ , X ₂ and X ₃ each independently represent -CO- or -SO ₂ -.

A ₂ represents a divalent linking group.

B represents a single bond, an oxygen atom or -N(Qx)-.

Qx represents a hydrogen atom or a monovalent organic group.

When B is -N(Qx)-, Q ₃ and Qx may be bonded to form a ring.

m represents 0 or 1.

Further, -NH- corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Specific examples of the compound (F) are listed below, but are not limited to these specific examples. Further, as a preferable specific example of the compound (F), in addition to the exemplified compound, a compound of (A-1) to (A-44) of the specification of the US Patent Application Publication No. 2010/0233629, or a US patent application can be cited. (A-1) to (A-23) of the specification of 2012/0156617 are disclosed.

[化128]

The molecular weight of the compound (F) is preferably from 500 to 1,000.

The photosensitive ray-sensitive or radiation-sensitive resin composition in the present invention may contain the compound (F) or may not contain the compound (F), and when the compound (F) is contained, the sensitizing ray-sensitive or radiation-sensitive resin composition The content of the compound (F) is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.1% by mass to 10% by mass based on the solid content.

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

The composition of the present invention may also have a nitrogen atom and have an action due to an acid The compound of the detached group (hereinafter also referred to as "compound (G)").

The group which is detached by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a semiamine acetal group. Carbamate group, half amine acetal ether group.

The molecular weight of the compound (G) having a group which is desorbed by the action of an acid is preferably from 100 to 1,000, more preferably from 100 to 700, particularly preferably from 100 to 500.

The compound (G) is preferably an amine derivative having a group which is desorbed by an action of an acid on a nitrogen atom.

The compound (G) may have a carbamate group having a protective group on a nitrogen atom. The protective group constituting the urethane group can be represented by the following formula (d-1).

In the formula (d-1), R _b each independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 10), a cycloalkyl group (preferably having a carbon number of 3 to 30), and an aryl group ( It is preferably a carbon number of 3 to 30), an aralkyl group (preferably having a carbon number of 1 to 10), or an alkoxyalkyl group (preferably having a carbon number of 1 to 10). R _b may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group or aralkyl group represented by R _b may be a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, a pendant oxy group, or the like, an alkoxy group, Halogen atom substitution. The same is true for the alkoxyalkyl group represented by R _b .

R _{b is} preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group. More preferably, it is a linear or branched alkyl group or a cycloalkyl group.

Examples of the ring formed by linking two R _{b to} each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.

The specific structure of the group represented by the general formula (d-1) is as disclosed in the paragraph [0466] of the specification of the US Patent Application Publication No. 2012/0135348A1, but is not limited thereto.

The compound (G) is particularly preferably a compound having a structure represented by the following formula (6).

In the formula (6), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When 1 is 2, two R _a may be the same or different, and two R _a may be bonded to each other and form a hetero ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.

The meaning of R _{b is the} same as R _b in the above formula (d-1), and preferred examples are also the same.

l represents an integer from 0 to 2, and m represents an integer from 1 to 3, and satisfies l+m=3.

In the formula (6), the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group as R _a may be substituted by a group which may be an alkyl group, a cycloalkyl group or an aryl group which may be an R _b group. The groups described for the substituted group of the aralkyl group are the same.

Preferred examples of the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group of the R _a (the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group may be substituted by the group) may be mentioned. The same base as the preferred example described for R _b .

Further, the hetero ring formed by linking R _{a to} each other preferably has a carbon number of 20 or less, and examples thereof include pyrrolidine, piperidine, morpholine, and 1,4,5,6-tetrahydropyrimidine. 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriene Azole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, carbazole, benzimidazole, imidazo[1,2- a]pyridine, (1S,4S)-(+)-2,5-diazabicyclo[2.2.1]heptane, 1,5,7-triazabicyclo[4.4.0]non-5-ene a base of a heterocyclic compound such as ruthenium, porphyrin, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline or 1,5,9-triazacyclododecane. a radical derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group One or more or one or more substituents of a functional group such as a morpholinyl group and a pendant oxy group are derived from a group derived from a group of the heterocyclic compound.

Specific examples of the particularly preferable compound (G) in the present invention include the compounds disclosed in paragraph [0475] of the specification of the U.S. Patent Application Publication No. 2012/0135348A1, but are not limited thereto.

The compound represented by the formula (6) can be synthesized in accordance with JP-A-2007-298569, JP-A-2009-199021, and the like.

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

The content of the compound (G) in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 0.001% by mass to 20% by mass, and more preferably 0.001% by mass based on the total solid content of the composition. 10% by mass, and more preferably 0.01% by mass to 5% by mass.

(4) strontium salt

Further, the composition of the present invention may further contain a phosphonium salt as a basic compound. Examples of the onium salt include an onium salt represented by the following formula (6A) or formula (6B). Due to the relationship with the acid strength of the photoacid generator generally used in the resist composition, it is expected that the cerium salt is controlled to diffuse the acid generated in the resist system.

In the formula (6A), Ra represents an organic group. However, the fluorine atom is substituted for the carbon atom directly bonded to the carboxylic acid group in the formula.

X ⁺ represents a phosphonium cation.

In the formula (6B), Rb represents an organic group. However, the fluorine atom is substituted for the carbon atom directly bonded to the sulfonic acid group in the formula.

X ⁺ represents a phosphonium cation.

The organic group represented by Ra and Rb is preferably a carbon atom directly bonded to a carboxylic acid group or a sulfonic acid group in the formula. However, in this case, in order to become an acid which is relatively weak compared with the acid generated from the photoacid generator, the fluorine atom is not substituted on the carbon atom directly bonded to the sulfonic acid group or the carboxylic acid group.

Examples of the organic group represented by Ra and Rb include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a carbon number of 7. ~30 aralkyl or a heterocyclic group having 3 to 30 carbon atoms. Some or all of the hydrogen atoms of the groups may be substituted.

Examples of the substituent which the alkyl group, the cycloalkyl group, the aryl group, the arylalkyl group, and the heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.

Examples of the phosphonium cation represented by X ⁺ in the general formulae (6A) and (6B) include a phosphonium cation, an ammonium cation, a phosphonium cation, a phosphonium cation, a diazonium cation, and the like. Among them, a phosphonium cation is more preferable. .

As the onium cation, for example, an aryl phosphonium cation having at least one aryl group is preferred, and a triaryl phosphonium cation is more preferred. The aryl group may have a substituent, and as the aryl group, a phenyl group is preferred.

As an example of the phosphonium cation and the phosphonium cation, a phosphonium cation structure of the formula (ZI) or a fluorene structure of the formula (ZII) in the compound (B) can also be preferably exemplified.

The specific structure of the onium salt represented by the general formula (6A) or the general formula (6B) is shown below.

When the composition of the present invention contains the onium salt represented by the formula (6A) or the formula (6B), the content of the composition is usually 0.01 based on the solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition. The mass % to 10% by mass, preferably 0.1% by mass to 5% by mass.

(5) Betaine compounds

Further, the composition of the present invention can also be preferably used in the formula (I) as disclosed in JP-A-2012-189977, and the formula (I) in JP-A-2013-6827. The compound represented by the formula (I) of the Japanese Patent Laid-Open Publication No. 2013-8020, Japanese Patent Laid-Open A compound having a sulfonium salt structure and an acid anion structure in one molecule, such as a compound represented by the formula (I), which is represented by the formula (I), and the like (hereinafter, also referred to as a betaine compound). The onium salt structure may, for example, be a phosphonium salt structure, a phosphonium salt structure or an ammonium salt structure, and is preferably a phosphonium salt structure or a phosphonium salt structure. Further, as the acid anion structure, a sulfonate anion or a carboxylate anion is preferred. As an example of this compound, the following examples are mentioned, for example.

[solvent]

Examples of the solvent which can be used in the preparation of the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention include an alkylene glycol monoalkyl ether carboxylate and an alkylene glycol monoalkyl ether. An alkyl lactate, an alkyl alkoxypropionate, a cyclic lactone (preferably having a carbon number of 4 to 10), a monoketone compound which may contain a ring (preferably having a carbon number of 4 to 10), and carbonic acid. An organic solvent such as an alkyl ester, an alkyl alkoxyacetate or an alkyl pyruvate.

Specific examples of such solvents include those described in the specification of the U.S. Patent Application Publication No. 2008/0187860 [0441] to [0455].

In the present invention, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent containing no hydroxyl group can be used as the organic solvent.

The solvent containing a hydroxyl group and a solvent containing no hydroxyl group can be appropriately selected from the above-exemplified compounds. The solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or an alkyl lactate, more preferably propylene glycol. Monomethyl ether (PGME (Propylene Glycol Monomethyl Ether), alias 1-methoxy-2-propanol), ethyl lactate. Further, as the solvent containing no hydroxyl group, an alkylene glycol monoalkyl ether acetate, an alkyl alkoxypropionate, a monoketone compound which may contain a ring, a cyclic lactone, an alkyl acetate is preferable. Ester, etc., among them, particularly preferred is propylene glycol monomethyl ether acetate (PGMEA (Propylene Glycol Monomethyl Ether Acetate), alias 1-methoxy-2-ethoxypropane), ethoxypropionic acid Ethyl ester, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, preferably propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, propyl carbonate, 2-heptanone .

The mixing ratio (mass) of the hydroxyl group-containing solvent to the hydroxyl group-free solvent is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferable.

The solvent is preferably propylene glycol monomethyl ether acetate, more preferably a single solvent of propylene glycol monomethyl ether acetate (PGMEA) or a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate (PGMEA). Preferable specific examples of the mixed solvent include a mixed solvent of PGMEA and a ketone solvent (cyclohexanone or 2-heptanone), and a mixture containing PGMEA and a lactone solvent (γ-butyrolactone). Solvent, package A mixed solvent containing PGMEA and PGME, including PGMEA. Ketone solvent. A solvent mixture of three solvents, a lactone solvent, containing PGMEA. PGME. A solvent mixture of three solvents, a lactone solvent, containing PGMEA. PGME. A mixed solvent of the three solvents of the ketone solvent, etc., but is not limited to these specific examples.

[Surfactant]

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a surfactant or may not contain a surfactant, and when a surfactant is contained, it is more preferably a fluorine-based surfactant and/or a lanthanide. Any one or two or more of a surfactant (a fluorine-based surfactant, a lanthanoid surfactant, and a surfactant containing both a fluorine atom and a ruthenium atom).

When the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, sensitivity, resolution, adhesion, and development defects are provided. Resist pattern.

Examples of the fluorine-based surfactant and/or the lanthanoid surfactant include the surfactants described in [0276] of the specification of the U.S. Patent Application Publication No. 2008/0248425, for example, Eftop EF301, EF303 (New Akita Chemicals ( Share) manufacturing), Fluorad FC430, 431, 4430 (Sumitomo 3M (manufactured by Sumitomo 3M) (shares), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (Di Aisheng (DIC) (shares) ) Manufacturing), Surflon S-382, SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), GF -300, GF-150 (Manufactured by East Asia Synthetic Chemicals Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 ( Mitsubishi Materials Electronics (Jemco) (manufactured by Jemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (made by Neos (shares)), etc. Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

Further, as the surfactant, in addition to the known surfactants as described above, the following surfactants may be used, which are utilized by a short-chain polymerization method (also referred to as a short-chain polymer method). Or a fluoroaliphatic group-derived polymer derived from a fluoroaliphatic compound produced by an oligomerization method (also referred to as an oligomer method). The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

As the surfactant compatible with the above, there are mentioned: Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Di Aisheng (share)), having a C ₆ F ₁₃ group a copolymer of acrylate (or methacrylate) and (poly(oxyalkylene)) acrylate (or methacrylate) having a C ₃ F ₇ -based acrylate (or methacrylate) and A copolymer of poly(oxyethylidene) acrylate (or methacrylate) and (poly(oxypropyl)) acrylate (or methacrylate).

Further, in the present invention, the fluorine-containing surfactant and/or the fluorine-containing surfactant described in [0280] of the specification of the US Patent Application Publication No. 2008/0248425 may be used. Or other surfactants other than lanthanide surfactants.

These surfactants can be used singly or in combination of several types.

When the sensitizing ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is preferably 0.0001 by mass relative to the total amount of the sensitizing ray-sensitive or radiation-sensitive resin composition (excluding the solvent). %~2% by mass, more preferably 0.0005% by mass to 1% by mass.

On the other hand, when the amount of the surfactant added is 10 ppm or less with respect to the total amount of the sensitizing ray-sensitive or radiation-sensitive resin composition (excluding the solvent), the surface bias of the hydrophobic resin is improved. Thereby, the surface of the resist film can be made more hydrophobic, and the water followability at the time of liquid immersion exposure can be improved.

The composition of the present invention can be prepared by appropriately mixing the above components. Further, at the time of preparation, the following steps may be carried out: a step of reducing metal impurities in the composition to a ppb level using an ion exchange membrane, a step of filtering impurities such as various particles using an appropriate filter, and a degassing step Wait. In the case of the above-mentioned steps, Japanese Patent Laid-Open No. 2012-88574, Japanese Patent Laid-Open No. 2010-189563, Japanese Patent Laid-Open No. 2001-12529, Japanese Patent Laid-Open No. 2001-350266, and Japanese JP-A-2002-99076, JP-A-H05-307263, JP-A-2010-164980, WO2006/121162A, JP-A-2010-243866, and JP-A-2010-020297 It is described in the bulletin and the like.

Further, the composition of the present invention preferably has a low water content. Specifically, in composition The water content of the total weight of the material is preferably 2.5% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.3% by mass or less.

<Composition for forming a protective film>

As described above, the pattern forming method of the present invention may include (10) a step of forming a protective film by the composition for forming a protective film between the step (1) and the step (2).

The protective film forming composition is preferably a second sensitizing ray-sensitive or radiation-sensitive resin composition different from the first sensitizing ray-sensitive or radiation-sensitive resin composition, and the second sensitizing ray or sensitizing radiation The resin composition contains a resin which decomposes due to the action of an acid and generates a polar group. That is, the pattern forming method of the present invention preferably includes (10') on the first sensitized ray-sensitive or radiation-sensitive film by a second different from the first sensitized ray-sensitive or radiation-sensitive resin composition. a step of forming a second sensitizing ray-sensitive or radiation-sensitive film composition by a sensitizing ray-sensitive or radiation-sensitive resin composition, the second sensitizing ray-sensitive or radiation-sensitive resin composition containing decomposition by an action of an acid A resin that produces a polar group. Thereby, in particular, in the step (3) of the second pattern forming method of the present invention, it is easy to more reliably remove the region above the exposed portion 11 of the protective film.

The resin in the second sensitizing ray-sensitive or radiation-sensitive resin composition, and the components which may be contained in the second sensitizing ray-sensitive or radiation-sensitive resin composition, and the second sensitizing ray The preferred range of the content of the total solid content of the radiation-sensitive resin composition is the same as that of the first sensitized ray-sensitive or radiation-sensitive resin composition. However, the second sensitizing ray or the radiation is linear The resin composition is different from the first sensitized ray-sensitive or radiation-sensitive resin composition. For example, even if the component contained in the first sensitizing ray-sensitive or radiation-sensitive resin composition is the same as the component contained in the second sensitizing ray-sensitive or radiation-sensitive resin composition, when the concentration of any one of the components is different The first sensitizing ray-sensitive or radiation-sensitive resin composition is also different from the second sensitizing ray-sensitive or radiation-sensitive resin composition.

When the pattern forming method of the present invention includes the step (10'), it is preferred that the resin (A) in the first sensitized ray-sensitive or radiation-sensitive resin composition contains a lactone structure, and the second sensitizing ray property Or the resin (A) in the radiation sensitive resin composition does not contain a lactone structure.

When the pattern forming method of the present invention includes the step (10'), it is preferably less susceptible to nucleophilic reaction from the surface treatment agent or the like, and further exhibits performance as a protective film, and is preferably a second sensitized ray. The resin (A) in the linear or translucent resin composition is substantially free of a repeating unit having a lactone structure (specifically, with respect to the resin in the second sensitizing ray-sensitive or radiation-sensitive resin composition (A) The content of the repeating unit having a lactone structure is preferably 10 mol% or less in all the repeating units in the).

The second sensitizing ray-sensitive or radiation-sensitive resin composition may contain an acid generator or may not contain an acid generator.

When the second sensitizing ray-sensitive or radiation-sensitive resin composition contains an acid generator, the resin (A) in the second sensitized ray-sensitive or radiation-sensitive resin composition can be produced from the acid generator Acid decomposes and produces polar groups.

On the other hand, even in the case where the second sensitizing ray-sensitive or radiation-sensitive resin composition does not contain an acid generator, the acid generator is used from the first sensitized ray-sensitive or radiation-sensitive resin composition. The generated acid diffuses from the first sensitizing ray-sensitive or radiation-sensitive film toward the second sensitized ray-sensitive or radiation-sensitive film, and the resin (A) in the second sensitized ray-sensitive or radiation-sensitive resin composition may also It decomposes by the diffused acid and generates a polar group.

The first sensitized ray-sensitive or radiation-sensitive film and the protective film are preferably less intermixed. In this regard, examples of the solvent which can be contained in the protective film-forming composition include an alcohol-based solvent, an ether-based solvent, and a combination thereof. Specific examples thereof include an alkyl group having 3 or more carbon atoms (more preferably 5 or more and 10 or less carbon atoms), a cycloalkyl group (preferably having a carbon number of 5 or more and 10 or less), and an aralkyl group. An alcohol (dialkyl ether or the like) of at least one of a group (preferably having a carbon number of 7 or more and 10 or less).

Further, the present invention contains the hydrophobic resin (HR) in the first sensitizing ray-sensitive or radiation-sensitive resin composition in the step (1), as described above, by making a hydrophobic resin (HR) The film is present in the surface layer of the film, and a film corresponding to the protective film may be formed. In this case, for the reason described above, it is preferred that the hydrophobic resin (HR) is a repeating unit which does not substantially contain a repeating unit having a lactone structure and which decomposes due to the action of an acid and generates a polar group. Resin.

Further, in the present invention, the top coat layer described in the step (2) may be a film corresponding to the protective film. In this case, for the reason described above, it is preferred that the top coat layer contains a resin which does not substantially contain a repeating form having a lactone structure. A resin containing a repeating unit which decomposes due to the action of an acid and generates a polar group.

[Examples]

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

. Synthesis example

Under a nitrogen gas stream, 40 g of a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether was placed in a three-necked flask, and heated to 80 ° C (solvent 1). The monomer corresponding to the repeating unit described below is dissolved in a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether in a ratio of 30/10/60 in a molar ratio of 30/10/60, respectively. Instead, a 22% by mass monomer solution (400 g) was prepared. In addition, a solution obtained by adding and dissolving 8 mol% of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) to the monomer was added dropwise to the solvent 1 over 6 hours. After completion of the dropwise addition, the reaction was further carried out at 80 ° C for 2 hours. After the reaction solution was allowed to stand for cooling and then poured into 400 ml of hexane 3600 ml/ethyl acetate, and the precipitated powder was filtered and dried, 74 g of a resin (P-1) was obtained. The obtained resin (P-1) had a weight average molecular weight of 12,000 and a degree of dispersion (Mw/Mn) of 1.6.

The resin (P-2) to the resin (P-11) were synthesized in the same manner as in the above-described synthesis example, except that the monomer corresponding to each repeating unit was used in such a manner that the desired composition ratio (mol ratio) was obtained. Hydrophobic resin (N-1) ~ hydrophobic resin (N-3).

[化135]

. Resist preparation

The components shown in the following Table 4 were dissolved in the solvent shown in the table and the total solid content concentration was changed to 3.5% by mass, and each was filtered by a polyethylene filter having a pore diameter of 0.05 μm. The resist composition Ar-1 to the resist composition Ar-17.

The abbreviations in Table 4 are as follows.

[resin]

The composition ratio (molar ratio), weight average molecular weight, and dispersity of the resin used in the examples are shown below.

[化137]

P-14: poly(dimethylaminoethyl methacrylate), Mw=15000, Mw/Mn=1.6

P-15: poly(4-vinylpyridine), Mw=60000, Mw/Mn=2.0

P-16: PAA-08 (made by Nittobo Medical Co., Ltd.) (polyallylamine)

4b: poly(2-ethylhexyl methacrylate), Mw=10000, Mw/Mn=1.5

[acid generator]

The structural formula of the acid generator is shown below.

[化138]

[alkaline compound]

The structural formula of the basic compound is shown below.

[化140]

[hydrophobic resin]

The composition ratio (mol ratio), weight average molecular weight, and degree of dispersion of the hydrophobic resin used in the examples are shown below.

[化141]

[Surfactant]

W-1: Megafac F176 (made by Di Ai Sheng (share)) (fluorine)

W-2: Megafac R08 (made by Di Ai Sheng (share)) (fluorine and lanthanide)

W-3: Polyoxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W-4: PolyFox PF-6320 (manufactured by Onofrio) (fluorine)

[solvent]

A1: Propylene glycol monomethyl ether acetate (PGMEA)

A2: γ-butyrolactone

A3: cyclohexanone

B1: Propylene glycol monomethyl ether (PGME)

B2: ethyl lactate

B3: 2-heptanone

B4: propyl carbonate

MIBC: methyl isobutyl methoxide

. Surface treatment preparation

The components shown in the following Table 5 were mixed, and each was filtered with a polyethylene filter having a pore diameter of 0.05 μm to prepare a surface treating agent S-1 to a surface treating agent S-10. Further, in Table 5, MIBC represents methyl isobutyl methanol.

. Performance evaluation

Using the prepared resist composition, a resist was formed by the following method pattern.

Example 1

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. A resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500/1100 manufactured by ASML), the numerical aperture is 0.75, the dipole, the outer sigma is 0.89, and the inner sigma is 0.65), and using an exposure mask (6% Half Tone Phase Shift Mask (HTPSM), line/space = 75 nm / 75 nm), the line width of the line pattern becomes 75 nm exposure amount The wafer is patterned for exposure. Thereafter, the film was heated at 100 ° C for 60 seconds, and the surface treatment agent S-1 was applied at a rotation speed of 1,500 rpm, and then baked at 100 ° C for 60 seconds, and the developer described in Table 6 was applied for 30 seconds. After development, the rinsing liquid described in Table 6 was used for laminating for 30 seconds, and then the wafer was rotated at 2000 rpm for 30 seconds, and then baked at 90 ° C for 60 seconds to obtain a line width. It is a resist pattern of 1:1 line and space of 75 nm.

Example 2

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. A resist composition Ar-2 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using ArF Excimer laser scanner (PAS5500/1100 manufactured by Esmol, 0.015, dipole, 0.89 for outer sigma, 0.65 for inner sigma) and using exposure mask (6% HTPSM, line/space) =75 nm / 75 nm), the obtained wafer was subjected to pattern exposure with a line width of the line pattern of 75 nm. Thereafter, the film was heated at 100 ° C for 60 seconds, and the surface treatment agent S-2 was applied at a rotation speed of 1,500 rpm, and then baked at 100 ° C for 60 seconds, and the peeling liquid described in Table 6 was applied for 30 seconds. The wafer was then rotated at 2000 rpm for 30 seconds. The developing solution described in Table 6 was coated for 30 seconds to carry out development, and after rinsing with the eluent described in Table 6 for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds, and then rotated. Baking was performed at 90 ° C for 60 seconds, thereby obtaining a 1:1 line and space resist pattern having a line width of 75 nm.

Example 3, Example 11, Example 12, Example 36, Example 37

A resist pattern of a 1:1 line and space having a line width of 75 nm was obtained in the same manner as in the method of Example 2 except that the resist, the surface treatment agent and the conditions described in Table 6 were used.

Example 4 to Example 10, Example 13, Example 35, and Comparative Example 1

A resist pattern of a 1:1 line and space having a line width of 75 nm was obtained in the same manner as in the method of Example 1 except that the resist, the surface treatment agent and the conditions described in Table 6 were used.

Example 14

The organic anti-reflection film ARC29SR (manufactured by Nissan Chemical Co., Ltd.) was applied to 12 The crucible wafer was baked at 205 ° C for 60 seconds to form an antireflection film having a film thickness of 95 nm. A resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser immersion scanner (XT1700i manufactured by Esmol, 1.02, C-Quad, 0.981 for outer sigma, 0.895 for inner sigma, XY bias) with an exposure mask ( 6% HTPSM, line/space = 65 nm / 65 nm), and the obtained wafer was subjected to pattern exposure with a line width of the line pattern of 65 nm. As the liquid immersion liquid, ultrapure water is used. Thereafter, the film was heated at 100 ° C for 60 seconds, and the surface treatment agent S-1 was applied at a rotation speed of 1,500 rpm, and then baked at 100 ° C for 60 seconds, and the developer described in Table 6 was applied for 30 seconds. After development, the rinsing liquid described in Table 6 was used for laminating for 30 seconds, and then the wafer was rotated at 2000 rpm for 30 seconds, and then baked at 90 ° C for 60 seconds to obtain a line width. It is a resist pattern of 1:1 line and space of 65 nm.

Example 15

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. A resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500/1100 manufactured by Esmol, 0.015, dipole, 0.89 for outer sigma, 0.65 for inner sigma), and using an exposure mask (6% HTPSM, line) /space = 75 nm / 75 nm), the obtained wafer was subjected to pattern exposure with a line width of the line pattern of 112.5 nm. Thereafter, After heating at 100 ° C for 60 seconds, the 2.38 wt% aqueous solution of TMAH was coated for 30 seconds to develop, and after rinsing with pure water for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds. After heating at 100 ° C for 60 seconds, the surface treatment agent S-1 was applied at a rotation speed of 1,500 rpm, and then baked at 100 ° C for 60 seconds, and the developer described in Table 6 was coated for 30 seconds to develop. After rinsing with the eluent liquid described in Table 6 for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds, and then baked at 90 ° C for 60 seconds, thereby obtaining a line width of 37.5 nm. The 1:1 line and space resist pattern.

Example 16

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. A resist composition Ar-2 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500/1100 manufactured by Esmol, 0.015, dipole, 0.89 for outer sigma, 0.65 for inner sigma), and using an exposure mask (6% HTPSM, line) /space = 75 nm / 75 nm), the obtained wafer was subjected to pattern exposure with a line width of the line pattern of 112.5 nm. Thereafter, the film was heated at 100 ° C for 60 seconds, and a 2.38 wt% aqueous solution of TMAH was applied for 30 seconds to carry out development, and after rinsing with pure water for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds. The mixture was heated at 100 ° C for 60 seconds, and the surface treatment agent S-2 was applied at 1,500 rpm, and then baked at 100 ° C for 60 seconds, and the peeling liquid described in Table 6 was applied for 30 seconds, and then at 2000 rpm. Rotating speed of the wafer 30 seconds. The developing solution described in Table 6 was coated for 30 seconds to carry out development, and after rinsing with the eluent described in Table 6 for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds, and then rotated. Baking was performed at 90 ° C for 60 seconds, thereby obtaining a 1:1 line and space resist pattern having a line width of 37.5 nm.

Example 17, Example 25, Example 26, Example 39, Example 40

A 1:1 line and space resist pattern having a line width of 37.5 nm was obtained in the same manner as in the method of Example 16 except that the resist, the surface treatment agent and the conditions described in Table 6 were used.

Example 18 to Example 24, Example 27, Example 38, and Comparative Example 2

A 1:1 line and space resist pattern having a line width of 37.5 nm was obtained in the same manner as in the method of Example 15 except that the resist, the surface treatment agent and the conditions described in Table 6 were used.

Example 28

An organic anti-reflection film ARC29SR (manufactured by Nissan Chemical Co., Ltd.) was applied onto a 12-inch-diameter silicon wafer, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 95 nm. A resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser immersion scanner (XT1700i manufactured by Esmol, 1.02, C-Quad, 0.981 for outer sigma, 0.895 for inner sigma, XY bias) with an exposure mask ( 6% HTPSM, line/space = 65nm/65nm), The line width of the line pattern becomes an exposure amount of 97.5 nm, and the obtained wafer is subjected to pattern exposure. As the liquid immersion liquid, ultrapure water is used. Thereafter, the film was heated at 100 ° C for 60 seconds, and a 2.38 wt% aqueous solution of TMAH (tetramethylammonium hydroxide) was applied for 30 seconds to carry out development, and after rinsing with pure water for 30 seconds, the solution was 2,000 rpm. The rotation speed of the wafer was rotated for 30 seconds, heated at 130 ° C for 60 seconds, and the surface treatment agent S-1 was applied at 1,500 rpm, and then baked at 100 ° C for 60 seconds to make the developer described in Table 6. The solution was applied for 30 seconds for development, and after rinsing with the eluent described in Table 6 for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds, and then baked at 90 ° C for 60 seconds. Thereby, a 1:1 line and space resist pattern having a line width of 32.5 nm was obtained.

Example 29

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. A resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500/1100 manufactured by Esmol, 0.015, dipole, 0.89 for outer sigma, 0.65 for inner sigma), and using an exposure mask (6% HTPSM, line) /Space = 75 nm / 75 nm), the obtained wafer was subjected to pattern exposure with a line width of the line pattern of 75 nm. After heating at 100 ° C for 60 seconds, it was exposed to a bottle with 100 g of surface treatment agent S-10 in a desiccator (23 ° C, 1 atm) and exposed to Post Exposure Delay for 1 hour. . Furthermore, baking was carried out at 100 ° C for 60 seconds to make the notes in Table 6. The developer was applied for 30 seconds to carry out development, and after rinsing with the eluent described in Table 6 for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds, and then at 90 ° C. Baking in seconds, thereby obtaining a 1:1 line and space resist pattern having a line width of 75 nm.

Example 30

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. A resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500/1100 manufactured by Esmol, 0.015, dipole, 0.89 for outer sigma, 0.65 for inner sigma), and using an exposure mask (6% HTPSM, line) /space = 75 nm / 75 nm), the obtained wafer was subjected to pattern exposure with a line width of the line pattern of 112.5 nm. Thereafter, the film was heated at 100 ° C for 60 seconds, and a 2.38 wt% aqueous solution of TMAH was applied for 30 seconds to carry out development, and after rinsing with pure water for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds. After heating at 100 ° C for 60 seconds, it was delayed in the desiccator (23 ° C, 1 atm) with a bottle which opened the bottle mouth and was added with 100 g of the surface treatment agent S-10, and was delayed by 1 hour. Furthermore, baking was carried out at 100 ° C for 60 seconds, and the developing solution described in Table 6 was applied for 30 seconds to carry out development, and after rinsing with the eluent described in Table 6 for 30 seconds, The wafer was rotated for 30 seconds at 2000 rpm and then baked at 90 ° C for 60 seconds, thereby obtaining a 1:1 line and space resist pattern having a line width of 37.5 nm.

Example 31

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. A resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500/1100 manufactured by Esmol, 0.015, dipole, 0.89 for outer sigma, 0.65 for inner sigma), and using an exposure mask (6% HTPSM, line) /Space = 75 nm / 75 nm), the obtained wafer was subjected to pattern exposure with a line width of the line pattern of 75 nm. Thereafter, the film was heated at 100 ° C for 60 seconds, and the surface treatment agent S-10 was applied at a number of revolutions of 1,500 rpm, and the developing solution described in Table 6 was applied for 30 seconds to develop, and the coating described in Table 6 was used. After the washing liquid was applied for 30 seconds for rinsing, the wafer was rotated at 2000 rpm for 30 seconds, and then baked at 90 ° C for 60 seconds, thereby obtaining a 1:1 line and space resistance with a line width of 75 nm. Etch pattern.

Example 32

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. A resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500/1100 manufactured by Esmol, 0.015, dipole, 0.89 for outer sigma, 0.65 for inner sigma), and using an exposure mask (6% HTPSM, line) / space = 75nm / 75nm), the line width of the line pattern changes The obtained wafer was subjected to pattern exposure at an exposure amount of 75 nm. Thereafter, the film was heated at 100 ° C for 60 seconds, and the surface treatment agent S-10 was applied at a rotation speed of 1,500 rpm, and then baked at 100 ° C for 60 seconds, and the developer described in Table 6 was applied for 30 seconds. Development was carried out, and the wafer was rotated at 2000 rpm for 30 seconds, and then baked at 90 ° C for 60 seconds, thereby obtaining a 1:1 line and space resist pattern having a line width of 75 nm.

Example 33

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. The resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a first resist film having a film thickness of 100 nm. Further, a resist composition Ar-14 was applied onto the first resist film, and baked at 100 ° C for 60 seconds to form a second resist film having a film thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500/1100 manufactured by Esmol, 0.015, dipole, 0.89 for outer sigma, 0.65 for inner sigma), and using an exposure mask (6% HTPSM, line) / space = 75 nm / 75 nm), the obtained wafer was subjected to pattern exposure with an exposure amount in which the line width of the line pattern of the first resist film became 112.5 nm. Thereafter, the film was heated at 100 ° C for 60 seconds, and a 2.38 wt% aqueous solution of TMAH was applied for 30 seconds to carry out development, and after rinsing with pure water for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds. After heating at 100 ° C for 60 seconds, the surface treatment agent S-1 was applied at a rotation speed of 1,500 rpm, and then baked at 100 ° C for 60 seconds, and the developer described in Table 6 was coated for 30 seconds to develop. Using the conditions described in Table 6 After the eluent was applied for 30 seconds to rinse, the wafer was rotated at 2000 rpm for 30 seconds, and then baked at 90 ° C for 60 seconds, thereby obtaining a 1:1 line with a line width of 37.5 nm. Space resist pattern.

Example 34

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 84 nm. A resist composition Ar-1 was applied onto the antireflection film, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500/1100 manufactured by Esmol, 0.015, dipole, 0.89 for outer sigma, 0.65 for inner sigma), and using an exposure mask (6% HTPSM, line) /space = 75 nm / 75 nm), the obtained wafer was subjected to pattern exposure with a line width of the line pattern of 112.5 nm. Thereafter, the film was heated at 100 ° C for 60 seconds, and a 2.38 wt% aqueous solution of TMAH was applied for 30 seconds to carry out development, and after rinsing with pure water for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds. Heating at 100 ° C for 60 seconds, and coating the surface treatment agent S-1 at 1500 rpm, and then baking at 100 ° C for 60 seconds, using a dry etching machine U-621 (Hitachi High-Technologies) The company manufactured), set the RF power to 800 W, set the chamber pressure to 4 Pa, set the substrate temperature to 50 ° C, and set the gas type and flow rate to Ar: 800 mL/min and C ₄ F ₆ : 40 mL/min, respectively. , O ₂ : 20 mL / min for 30 seconds dry etching. Then, after the MIBC was applied for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds, and the developing solution described in Table 6 was applied for 30 seconds to develop, and the eluent liquid coating described in Table 6 was used. After rinsing for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds, and then baked at 90 ° C for 60 seconds, thereby obtaining a 1:1 line and space resist pattern having a line width of 37.5 nm. .

Further, in all of the examples, a surface treatment agent which sufficiently covers the resist film on the substrate and the amount of the first pattern is used.

In Table 6, PB represents heating before exposure, and PEB represents heating after exposure. Further, in the column of PB, PEB, and pre-baking and surface-treating, for example, "100 ° C, 60 s" means heating at 100 ° C for 60 seconds. EEP represents ethyl-3-ethoxypropionate.

. Pattern top view

The line pattern in the pattern formation region in the wafer of each of the examples was scanned in the longitudinal direction using an Atomic Force Microscopy (AFM) manufactured by Veeco Co., Ltd. (trade name: Nanoscope 4). The results obtained by extracting the height information at the top of the pattern and calculating the average surface roughness are shown in Table 7. The smaller the average surface roughness at the top of the pattern, the flatter the top of the pattern.

. Pattern residual observation during double development

The line pattern in the pattern forming region in the wafer of each of the examples was scanned in the longitudinal direction using AFM (trade name: Nanoscope 4) manufactured by Wolters Co., Ltd. The results obtained by calculating the difference between the average height of the top of the pattern and the average height of the bottom of the pattern are shown in Table 7. The larger the difference, the better the residualness of the pattern.

. Observation of Solvent Solubility of Solvents in Surface Treatment Agents

Each resist composition Ar-1 to resist composition Ar-17 was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 100 ° C for 60 seconds to form a film thickness. It is a 100 nm resist film. The obtained wafer was immersed in a solvent for various surface treatment agents at 23 ° C for 30 seconds, and dried to measure the thickness of the residual film. The results obtained by calculating the value ([nm/s]) calculated by (100-residual film thickness [nm]) ÷30 as the dissolution rate of the film with respect to the solvent are shown in Table 7.

From the results shown in the table, it is understood that Example 1 to Example 14, Example 29, and implementation of the first pattern forming method of the present invention were performed as compared with Comparative Example 1 in which step (4A) was not performed. The pattern tops of Example 31, Example 32, and Example 35 to Example 37 were excellent in flatness. In addition, it is understood that the flatness of the pattern top of Examples 1 to 14 using a surface treatment agent containing a solvent is particularly excellent.

Further, it is understood that Example 15 to Example 28, Example 30, Example 33, Example 34, and implementation of the second pattern forming method of the present invention were performed as compared with Comparative Example 2 in which Step (B) was not performed. The flatness of the pattern top of Examples 38 to 40 and the pattern remnancy at the time of double development were excellent. In addition, it is understood that the flatness of the pattern top and the pattern remnancy at the time of double development of Examples 15 to 28 using the surface treatment agent containing a solvent are particularly excellent.

Although the embodiment has been described above, it is considered that the invention of the present application is not limited to the embodiments, and for example, the pattern may be formed even in the following embodiment.

. In the developing solution containing an organic solvent in each of the examples, a form of negative development is added by adding a nitrogen-containing basic compound such as trioctylamine of about 1% by mass.

. In each of the embodiments, the exposure using the ArF excimer laser is replaced with the EUV exposure, and further, as the resin in the resist composition, it is suitable as the "especially suitable for EUV exposure or electron beam exposure. Introduction of resin used in the ground The form of the resin (resin containing a repeating unit having an aromatic ring) and the like.

[Industrial availability]

According to the present invention, it is possible to provide a pattern forming method capable of forming a pattern having excellent flatness at the top of a pattern or a pattern at the time of double development, a surface treating agent therefor, a method for producing an electronic device, and an electronic device.

While the invention has been described in detail with reference to the specific embodiments the embodiments

The present application is based on a Japanese patent application filed on August 2, 2013 (Japanese Patent Application No. 2013-161901), and a Japanese patent application filed on January 20, 2014 (Japanese Patent Application No. 2014-007907) This is incorporated herein by reference.

1‧‧‧Substrate

2‧‧‧Photosizing ray-sensitive or radiation-sensitive linear film

Claims (16)

A pattern forming method comprising: (1) a step of forming a sensitized ray-sensitive or radiation-sensitive film by a sensitizing ray-sensitive or radiation-sensitive resin composition, the sensitizing ray or a radiation-induced linearity The resin composition contains a resin which decomposes due to the action of an acid and generates a polar group; (2) a step of exposing the sensitizing ray-sensitive or radiation-sensitive film; (4A) containing and exposing the resin after exposure a step of treating a surface of the compound in which the polar group interacts with the photosensitive ray-sensitive or radiation-sensitive film; and (5A) using the developing solution containing the organic solvent for the sensitized ray-sensitive or radiation-sensitive film The step of developing. A pattern forming method comprising: (1) a step of forming a sensitized ray-sensitive or radiation-sensitive film by a sensitizing ray-sensitive or radiation-sensitive resin composition, the sensitizing ray or a radiation-induced linearity The resin composition contains a resin which decomposes due to the action of an acid and generates a polar group; (2) a step of exposing the sensitizing ray-sensitive or radiation-sensitive film; and (3) sensitizing the photosensitive developer a step of developing a radiant or radiation sensitive film to obtain a first developing pattern; (4B) applying a surface treating agent containing a compound that interacts with a polar group possessed by the exposed resin to the first developing pattern And (5B) further developing the first developing pattern using a developing solution containing an organic solvent to obtain a second developing pattern. The pattern forming method according to claim 2, wherein between the step (2) and the step (3), (6) heating the sensitized ray-sensitive or radiation-sensitive film And the step (3) between the step (3) and the step (4B), comprising (7) the first development pattern at a temperature higher than a temperature of 30 ° C or higher than the temperature of the heating in the step (6) The step of heating. The pattern forming method according to claim 2, wherein between the step (4B) and the step (5B), the step of heating the first developing pattern is included (8). The pattern forming method according to any one of claims 1 to 4, wherein the surface treatment agent contains a basic compound as the compound which interacts with a polar group. The pattern forming method according to claim 5, wherein the surface treatment agent contains, as the basic compound, a repeating unit having a basic functional group. The pattern forming method according to claim 5, wherein the basic compound contains a heteroaryl group selected from the group consisting of a tertiary amino group, a quaternary ammonium group, and a heteroaryl group which may have a substituent and has a nitrogen atom as a ring member. At least one of the group consisting of. The pattern forming method according to any one of claims 1 to 4, wherein the compound which interacts with a polar group is soluble in the step (5A) or the step (5B) In a developer containing an organic solvent. The pattern forming method according to any one of claims 1 to 4, wherein the surface treatment agent contains a solvent, the step (4A) or the step The step (4B) includes a step of bringing the surface treatment agent into contact with the surface of the sensitizing ray-sensitive or radiation-sensitive film. The pattern forming method according to claim 9, wherein the solvent contained in the surface treatment agent is used at 23 ° C when the unexposed coating film contacting the sensitizing ray-sensitive or radiation-sensitive film is used. The solvent having a film dissolution rate of 0.1 nm/s or less. The pattern forming method according to any one of claims 1 to 4, wherein the step (4A) or the step (4B) comprises contacting the vapor of the surface treatment agent with the sensitization The step of radiant or sensitizing the surface of the radiation film. The pattern forming method according to any one of claims 1 to 4, wherein the exposure is a liquid immersion exposure. A method of producing an electronic component, comprising the pattern forming method according to any one of claims 1 to 4. An electronic component manufactured by the method of manufacturing an electronic component according to claim 13 of the patent application. A surface treatment agent for use in the pattern forming method according to any one of claims 1 to 4. A surface treatment agent comprising a resin and a solvent containing a monohydric alcohol, the resin containing a repeating unit having a basic functional group.