TW201523699A - Pattern forming method and method for producing electronic device - Google Patents

Abstract

A pattern forming method of the invention includes: a step A, forming a pattern 1 including an organic substance on a substrate; a step B, forming a film 2 covering the pattern 1; and a step C, removing a portion of the film 2 by etching the film 2 through cluster ions, so as to expose at least one portion of the pattern 1.

Description

Pattern forming method, method of manufacturing electronic component

The present invention relates to a semiconductor manufacturing step applicable to an integrated circuit (IC), a circuit substrate such as a liquid crystal or a thermal head, and further lithography of photofabrication. A pattern forming method of the step and a method of manufacturing the electronic component. In particular, there is a pattern forming method suitable for exposing an ArF exposure apparatus using a far ultraviolet light having a wavelength of 300 nm or less as a light source, and a method of manufacturing 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.

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 to further improve the resolution, it is advocated between the projection lens and the sample. A method of filling a liquid having a high refractive index (hereinafter also referred to as "liquid immersion liquid") (that is, a liquid immersion method). In addition, Extreme Ultraviolet (EUV) lithography that uses a shorter wavelength (13.5 nm) of ultraviolet light for exposure is also advocated.

Recently, attempts have been made in large numbers not only by the short wavelength of the exposure light source and the high numerical aperture (high NA) of the projection lens, but also by performing various steps (processes), for example, the formed resistance. The etchant pattern is subjected to various physical treatments and chemical treatments to obtain fine pattern sizes above the optical resolution limit.

For example, there is a pattern forming method described in Patent Document 1. More specifically, the pattern forming method is (1) a step of forming a resist pattern on a substrate, (2) a step of forming a crosslinked layer in a manner of covering the resist pattern, and (3) by dry etching. Removing the portion of the formed crosslinked layer formed on the upper portion of the resist pattern, (4) removing the resist pattern, and leaving the crosslinked layer formed on the side of the resist pattern, leaving the residual intersection The layer is used as the final mask pattern.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2010-534306

However, in this technique, in particular, the dry etching of the above (3) requires removal of the crosslinked layer, and on the other hand, there is a concern that the dry etching causes an unexpected modification (hardening) of the resist pattern on the substrate, For example, there is a fear that the removal of the resist pattern is not sufficiently performed, thereby causing problems such as bridging defects. In order to reduce this concern and Applying the technology to actual mass production requires further improvements.

The present invention has been made in view of the above problems, and an object thereof is to provide a pattern forming method which is less likely to cause defects.

The inventors of the present invention have conducted intensive studies on the problems of the prior art, and as a result, have found that the above problems can be solved by performing an etching treatment using cluster ions.

That is, it was found that the object can be attained by the following constitution.

(1) A pattern forming method comprising: step A, forming a pattern 1 containing an organic substance on a substrate; step B, forming a film 2 covering the pattern 1; and step C, etching the film 2 by a cluster ion etching A portion of the pattern 1 is removed such that at least a portion of the pattern 1 is exposed.

(2) The pattern forming method according to (1), further comprising the step D of remaining the film 2 and removing at least a portion of the pattern 1 after the step C.

(3) The pattern forming method according to (1) or (2), wherein the step A includes a step of forming the film 1 on the substrate using a photosensitive ray-sensitive or radiation-sensitive resin composition, and irradiating the film 1 with the actin The step of ray or radiation, and the step of developing the film 1 after irradiation to form the pattern 1.

(4) The pattern forming method according to (3), wherein the sensitizing ray-sensitive or radiation-sensitive resin composition is a composition containing a resin whose polarity is increased by the action of an acid.

(5) The pattern forming method according to (3) or (4), wherein the development of the film 1 is carried out using an aqueous alkaline solution.

The pattern forming method according to any one of (1) to (5), wherein the step B contains a step of applying the composition used in the formation of the film 2 to the pattern 1.

(7) The pattern forming method according to (6), wherein the composition used for forming the film 2 is a composition containing a film forming component and an organic solvent.

(8) The pattern forming method according to (7), wherein the organic solvent contains at least one of an alcohol solvent and an ether solvent.

The pattern forming method according to any one of (2) to (8), wherein the step D includes a step of removing at least a portion of the pattern 1 by a treatment liquid containing an organic solvent.

(10) A method of producing an electronic component, comprising the pattern forming method according to any one of (1) to (9).

According to the present invention, it is possible to provide a pattern forming method which is difficult to produce defects.

10‧‧‧Substrate

12‧‧‧ Pattern 1

14‧‧‧ membrane 2

16‧‧‧Interaction membrane

Fig. 1 is a schematic cross-sectional view showing the procedure of each step of an embodiment of the pattern forming method of the present invention in order.

Fig. 2 is a schematic cross-sectional view showing the procedure of each step of another embodiment of the pattern forming method of the present invention in order.

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

In the present specification, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene oxime. And methacryl oxime.

One of the features of the present invention is a point at which an etching treatment using cluster ions is performed. The mechanism of the present invention can be estimated as follows.

As described above, Patent Document 1 employs one of the crosslinked layers by dry etching. Partial removal method. However, at the time of the dry etching, ions penetrate the crosslinked layer to reach a resist pattern disposed at a lower portion of the crosslinked layer, resulting in modification (for example, carbonization) of the resist pattern. As a result, the resist pattern cannot be removed in the removal method using a solvent or the like, and the desired pattern cannot be obtained. On the other hand, when the etching by the cluster ions is performed, the cluster ions irradiated to the film 2 as an object to be etched are difficult to penetrate the film 2 due to the properties thereof, and as a result, the pattern 1 can be suppressed from being modified to obtain a desired pattern.

The pattern forming method of the present invention has at least the following three steps.

Step A: Step of forming a pattern 1 containing an organic substance on a substrate

Step B: Step of forming the film 2 covering the pattern 1

Step C: a step of removing a portion of the film 2 by the cluster ion etching film 2, thereby exposing at least a portion of the pattern 1

Furthermore, it is preferred to carry out the steps A to C in the order of step A to step C.

Further, in addition to the above steps A to C, it is preferable to further include the following step D after the step C.

Step D: Step of leaving film 2 and removing at least a portion of pattern 1 after step C

Fig. 1 is a schematic cross-sectional view showing the procedure of each step of an embodiment of the pattern forming method of the present invention in order. Hereinafter, the procedure of each step of the pattern forming method will be described in detail with reference to (A) to (E) of FIG. 1 . In addition, in one embodiment (A) to (E) of FIG. 1, an embodiment of the pattern forming method including the above steps A to D will be described in detail.

<Step A>

Step A is a step of forming a pattern 1 containing an organic substance on a substrate. By performing this step, the pattern 1 (12) can be formed on the substrate 10 as shown in (A) of FIG. Further, in FIG. 1(A), the pattern 1 (12) is arranged in a stripe shape, but is not limited to this form, and various pattern shapes can be adopted.

The specific procedure of the step A is not particularly limited to the pattern forming method or the material used as long as the pattern 1 containing the organic substance can be formed. For example, (1) patterning the film 1 obtained by using a photosensitive ray-sensitive or radiation-sensitive resin composition, and performing development processing using a suitable developing solution, thereby forming a pattern 1; (2) by so-called Nano-imprint technology to form pattern 1 (for example, refer to "Basic and Technology Development of Nano Imprinting ‧ Application Development - Substrate Technology and Latest Technology Development of Nano Imprinting -", Editor: Hirai Yoshihiko, Frontier (3) Form 1 is formed by so-called self-organized pattern formation (Directed Self Assembly (DSA)) (for example, refer to Japanese Patent Laid-Open Publication No. 2008-036491, " Methods such as Proceedings of The International Society for Optical Engineering, Proceedings of SPIE, Vol. 7637, 76360G-1, etc.). Further, this step may further include a step of improving the surface roughness of the pattern as described in, for example, Japanese Patent Laid-Open No. 2004-235468 and Japanese Patent Laid-Open No. Hei No. 2005-19969.

In the above, it is preferable that the film 1 obtained by using the sensitizing ray-sensitive or radiation-sensitive resin composition is subjected to pattern exposure in the aspect of controlling the shape of the obtained pattern 1 more easily, and is utilized. Proper developer for development processing, borrowing This forms pattern 1. Hereinafter, the method will be described in detail.

More specifically, the method of the above (1) is preferably a step of forming a film 1 on a substrate by using a sensitizing ray-sensitive or radiation-sensitive resin composition (hereinafter, also simply referred to as "composition"); The step of irradiating the film 1 with actinic rays or radiation; and developing the film 1 after the irradiation to form the pattern 1. The following steps are divided into the following three procedures for detailed description.

(Step X) A step of forming a film 1 on a substrate using a sensitizing ray-sensitive or radiation-sensitive resin composition

(Step Y) Step of irradiating the film 1 with actinic rays or radiation

(Step Z) Step of Developing Film 1 to Form Pattern 1

Further, the photosensitive ray-sensitive or radiation-sensitive resin composition used in the above step X will be described in detail later. Further, the film 1 formed in the step A (step X, step Y, and step Z) is also simply referred to as "film" hereinafter.

(Step X)

Step X is a step of forming a film on a substrate using a sensitizing ray-sensitive or radiation-sensitive resin composition.

The method of forming a film on a substrate by using a sensitizing ray-sensitive or radiation-sensitive resin composition is not particularly limited, and a known method can be employed. In addition, in terms of adjusting the thickness of the film more easily, a method of forming a film by applying a sensitizing ray-sensitive or radiation-sensitive resin composition to a substrate is exemplified.

Further, the coating method is not particularly limited, and a known method can be employed. Among them, a spin coat can be preferably used in the field of semiconductor manufacturing.

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), a semiconductor manufacturing step such as IC, and a liquid crystal can be used. A manufacturing step of a circuit board such as a thermal head, and a substrate generally used in a lithography step of another photosensitive etching process. Further, an organic anti-reflection film may be formed between the film and the substrate as needed.

It is also preferable to include a pre-heating step (Prebake (PB)) before the film formation and before the step Y described later.

Further, after the step Y and before the step Z, it is also preferable to include a post-exposure heating step (Post Exposure Bake (PEB)).

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 components provided in the developing machine are carried out, and may be performed using a hot plate or the like. The reaction of the exposed portion is promoted by baking, and the sensitivity or pattern outline is improved.

The film (resist film) formed using the sensitizing ray-sensitive or radiation-sensitive resin composition preferably has a receding contact angle of 70° or more at a temperature of 23±3° C. and a humidity of 45±5%, and is suitable for passage via In the case where the liquid immersion medium is exposed, the receding contact angle of the film (resist film) is more preferably 75° or more, and particularly 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 better receding contact angle, it is preferred to use the sensitizing ray or the sensation The radioactive resin composition contains a hydrophobic resin to be described later. Alternatively, a coating layer (so-called "top-coat") formed of a hydrophobic resin composition may be formed on the resist film, thereby increasing the receding contact angle.

The thickness of the resist film is not particularly limited, and from the viewpoint of forming a fine pattern having a further high precision, it is preferably 1 nm to 500 nm, more preferably 1 nm to 100 nm.

(Step Y)

Step Y is a step of irradiating the film obtained in the step X with actinic rays or radiation (hereinafter, "irradiation of actinic rays or radiation" is simply referred to as "exposure"). More specifically, the step of selectively exposing the film in a manner of forming a desired pattern. Thereby, the film is exposed in a pattern shape and only the solubility of the exposed portion of the film changes.

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

The method of selectively exposing the film is not particularly limited, and a known method can be used. For example, a binary mask (Binary-Mask) having a light-shielding portion of 0% or a halftone type phase shift mask having a transmittance of 6% at a light-shielding portion (HT-Mask) can be used. ).

Binary masks can generally be used to form chromium films and chromium oxide films on quartz glass substrates. As a light-shielding part.

The halftone phase shift mask can generally be used as a light shielding portion for forming a moSi (molybdenum silicide) film, a chromium film, a chromium oxide film, a hafnium oxynitride film, or the like on a quartz glass substrate.

Further, in the present invention, it is not limited to the exposure by the mask, and the exposure without the mask may be performed. For example, selective exposure (pattern exposure) may be performed by drawing with an electron beam or the like.

This step Y can include multiple exposures.

In addition, a liquid immersion exposure method can be applied in the step Y. 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 film on the wafer and can ignore the effect on the optical coating on the lower surface of the lens element. By.

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 a substance which is opaque to light of 193 nm or an impurity which is different in refractive index from water is mixed, deformation of an optical image projected on the resist is caused, so that water used is used. Good for distilled water. 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.

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.

(Step Z)

Step Z is a step of developing the film to form the pattern 1. By carrying out this step, the desired organic-containing pattern 1 can be formed.

The type of the developer to be used for development is not particularly limited, and for example, an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as "organic developer") can be used.

As the alkaline developing solution, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, and diethylamine can be used. Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide , tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraamylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltetramethyl hydroxide Tetraalkylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, and hydroxide III, such as ammonium amide, methyl amyl ammonium hydroxide, dibutyl diamyl ammonium hydroxide An alkaline aqueous solution such as a quaternary ammonium salt such as ethylbenzylammonium or a cyclic amine such as pyrrole or piperidine. Further, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution for use. The alkali concentration of the alkaline developer is usually from 0.1% by mass to 20% by mass. The pH of the alkaline developer is usually from 10.0 to 15.0. The alkali concentration and pH of the alkaline developer can be appropriately adjusted and used. The alkaline developer may also be added by using a surfactant or an organic solvent.

As the eluent in the rinsing treatment after the alkali development, pure water may be used, or an appropriate amount of a surfactant may be added and used.

Further, after the development treatment or the rinsing treatment, a treatment for removing the developer or eluent adhering to the pattern by the supercritical fluid can be performed.

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, acetyl carbitol, acetophenone, methyl naphthyl 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-ethoxy propionate, 3-methyl Oxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactate Ester, methyl 2-hydroxyisobutyrate, 3-methylbutyl acetate, 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.

Examples of the amide-based solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and hexamethylphosphonium triamine. , 1,3-dimethyl-2-imidazolidinone, and the like.

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

The solvent may be mixed in a plurality of types, or may be used in combination with a solvent or water other than the above. In order to sufficiently obtain the effects of the present invention, the water content of the entire developer is preferably less than 10% by mass, and more preferably substantially no 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.

In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

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 surfactant and/or the lanthanoid surfactant include Japanese Patent Laid-Open No. 62-36663. Japanese Patent Laid-Open Publication No. SHO 61-226746, Japanese Patent Laid-Open No. Sho 61-226745, Japanese Patent Laid-Open No. Sho 62-170950, Japanese Patent Laid-Open No. SHO63-34540, Japanese Patent Laid-Open Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The surfactants described in the specification of U.S. Patent No. 5,529,881, U.S. Patent No. 5,296,330, U.S. Patent No. 5, 460, 098, U.S. Patent No. 5,576, 143, U.S. Patent No. 5,294, 511, and U.S. Patent No. 5,824,451 are preferred. It is a nonionic surfactant. The nonionic surfactant is not particularly limited, but a fluorine-based surfactant or a lanthanoid surfactant is more preferably used.

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.

The organic developer may also contain a basic compound. Examples of the basic compound include a nitrogen-containing basic compound, and examples thereof include a nitrogen-containing compound described in JP-A-2013-11833, in particular, <0021> to <0063>. 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 organic solvent contained in the developer, it is preferred to use a substance having a reduced peroxide content, whereby the storage stability of the sensitizing ray-sensitive or radiation-sensitive resin composition can be improved. The content of the peroxide in the organic solvent is preferably 2.0. It is preferably mmol% or less, more preferably 1.0 mmol% or less, still more preferably 0.5 mmol% or less, and particularly preferably contains no peroxide.

Further, the organic solvent to be used as the eluent to be described later, the organic solvent contained in the sensitizing ray-sensitive or radiation-sensitive resin composition, and the organic solution contained in the spacer-forming composition are also preferably The content range of the peroxide is satisfied.

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.

When the various developing methods include a step of ejecting the developing solution from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developing solution (the flow rate per unit area of the ejected developing solution) is preferably 2 mL/sec/mm ² or less is more preferably 1.5 mL/sec/mm ² or less, and 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.

By setting the discharge pressure of the developer to be ejected to the above range, pattern defects derived from the resist residue after development can be remarkably reduced.

Although the details of the mechanism are not determined, the reason for this is that the pressure of the developer applied to the resist film is reduced by setting the discharge pressure to the above range, and the resist film can be suppressed. The pattern of the agent is inadvertently cut or collapsed.

Further, the discharge pressure (mL/sec/mm ² ) of the developer is a value in the developing nozzle outlet in the developing device.

The method of adjusting the discharge pressure of the developer, for example, a method of adjusting the discharge pressure by a pump or the like, or a method of adjusting the discharge pressure by adjusting the pressure from the supply of the pressure tank, and the like.

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.

In the step Z, a step of developing using a developing solution containing an organic solvent (organic solvent developing step) and a step of developing using an alkaline aqueous solution (alkali developing step) may be used in combination. Thereby, a finer pattern can be formed.

In the present invention, the portion having weak exposure intensity is removed by the organic solvent development step, but the portion having high exposure intensity can be further removed by performing the alkali development step. By performing the multiple development process for performing multiple developments in this way, only the region of the intermediate exposure intensity can be patterned in an insoluble manner, so that a more fine pattern can be formed (in Japanese Patent Laid-Open Publication No. 2008-292975, <0077> The same mechanism).

In the pattern forming method of the present invention, the order of the alkali developing step and the organic solvent developing step is not particularly limited, but it is more preferable to perform alkali development before the organic solvent developing step.

It is preferred to include a step of washing with an eluent (rinsing step) after the alkali development step and/or the organic solvent development step.

The eluent used in the elution step is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. As The eluent preferably contains at least one selected from the group consisting of a hydrocarbon solvent (for example, undecane), a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. An organic 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 particular, it is more preferred to carry out the step of washing with 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. The step of washing with an eluent containing an alcohol solvent or an ester solvent is particularly preferably a step of washing with an eluent containing a monohydric alcohol, and it is preferable to use a monohydric alcohol having a carbon number of 5 or more. The step of washing the eluent.

Here, examples of the monohydric alcohol used in the elution step include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, and 3-methyl- can be used. 1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, Cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., as a particularly preferred monohydric alcohol having 5 or more carbon atoms. -hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

Each component may be used in combination of 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. Next, it is 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 rinsing step, the rinsing liquid is used to carry out the cleaning treatment. 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 impurities It is preferable to use a Teflon (registered trademark) filter, a polyolefin filter, an ion exchange filter, etc., and it is preferable to manufacture these chemical liquids in a clean room. Filtration of the filter, etc., while reducing 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. Examples of such a container include a container in which the inner wall of the container is a perfluoro resin (for example, a Fluoro Pure perfluoroalkoxy (PFA) composite barrel manufactured by Entegris Co., Ltd. Surface: PFA resin lining), steel cans manufactured by JFE Co., Ltd. (liquid inner surface: zinc phosphate film), and the like.

<Step B>

Step B is a step of forming the film 2 covering the pattern 1. More specifically, as shown in FIG. 1(B), the film 2 (14) is disposed so as to cover the surface of the pattern 1 (12) that is not in contact with the substrate 10. Further, in FIG. 1(B), the film 2 is disposed so as to fill the gap of the pattern 1, but the film 2 is not limited thereto. The film 2 may not be filled with the pattern as long as the film 2 covers the pattern 1 . 1 gap.

The method of forming the film 2 is not particularly limited, and the film 2 can be formed by bringing a film forming component (hereinafter also referred to as a "spacer agent") used for forming the film 2 into contact with the pattern 1. As a contact method of a film forming component, for example, it can be applied to have a pattern 1 A method in which a substrate is immersed in a bath filled with a film forming component for a fixed period of time (dipping method); a method in which a film forming component is deposited on the surface of the pattern 1 by a surface tension and is stationary for a fixed period of time (developing a puddle) Method for spraying a film forming component onto the surface of the pattern 1 (spray method); a method of continuously ejecting a film forming component onto a pattern 1 of a substrate having a pattern 1 that is rotated at a fixed speed while scanning a discharge nozzle at a fixed speed (Dynamic distribution method); a method of applying a film forming component to the pattern 1 to form the film 2 on the pattern 1, a method of exposing the pattern 1 to the vapor of the film forming component, and the like.

When the film 2 is formed, it is preferred to cause an interaction between the pattern 1 and the film forming component. For example, in the case where the photosensitive ray-sensitive or radiation-sensitive resin composition used in the formation of the pattern 1 contains a resin which decomposes due to the action of an acid and generates a polar group, it is preferably used between the polar group and the polar group. A film-forming component that produces an interaction (for example, a chemical bond, an electrostatic interaction, a hydrogen bond, a dipole interaction, a coordination bond, etc. Further, in the present specification, a chemical bond is also one of the interactions). When such an interaction occurs, the resin in the pattern 1 and the film forming component in the film 2 interact between the pattern 1 and the film 2 to form an interaction film. The interaction film is a film formed by the contact of the pattern 1 with the film 2, and thus can be a finer pattern. Further, since the solubility of the interaction film with respect to the solvent is different from the solubility of the pattern 1 and the film 2 with respect to the solvent, the remaining pattern 1 and the remaining film 2 can be removed as described later, and only the substrate can be used. The interaction membrane remains.

Further, a film forming component which does not cause the interaction as described above can also be used.

Further, the film forming component itself may be a component to be crosslinked.

As a method of forming the film 2, in terms of easily controlling the film thickness of the film 2, the composition used in the formation of the film 2 is preferable (hereinafter, also referred to as "the composition for forming a spacer". The method of forming the film 2 by applying it on the pattern 1 (hereinafter also referred to as "coating method"). The form of the coating method will be described in detail below.

The method of applying the composition for forming a spacer is not particularly limited, and a known method can be used. For example, spin coating can be preferably used.

The type of the component contained in the spacer-forming composition is not particularly limited as long as it contains a component capable of forming the film 2, but it is preferably in terms of line width uniformity of the formed pattern. It contains a film forming component and an organic solvent.

Further, water may be contained in the spacer-forming composition, but the water content is preferably 10% by mass with respect to the total mass of the spacer-forming composition in terms of line width uniformity of the formed pattern. % or less, more preferably 5% by mass or less. Further, the water content is, in other words, the content (% by mass) of water contained in the composition with respect to the total mass of the composition.

Details of the film forming component will be described in detail later.

The type of the organic solvent contained in the composition for forming a spacer is not particularly limited, and a known organic solvent can be used. For example, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, an ether solvent, or the like, or a hydrocarbon solvent exemplified in the organic developer used in the step S, may be mentioned. The illustration of each solvent is as described above. In particular, at least one of an alcohol solvent and an ether solvent is preferred in terms of the shape of the pattern to be formed.

The content of the film-forming component and the organic solvent in the spacer-forming composition is not The content of the organic solvent is preferably from 700 parts by mass to 8,000 parts by mass, more preferably from 1,500 parts by mass to 3,000 parts by mass, per 100 parts by mass of the film-forming component.

In the step B, it is preferred to apply a composition for forming a spacer as described above, and to provide a heating step for performing heat treatment before step C to be described later. The heat treatment can promote the interaction between the pattern 1 and the film 2 while the hardening of the film 2 itself progresses.

Further, the conditions of the heat treatment are not particularly limited, and the optimum conditions can be appropriately selected depending on the type of the material used in the pattern 1 and the film 2, but the heating temperature is preferably 70 ° C to 200 ° C, more preferably 90 ° C. ~160 ° C, the heating time is preferably from 10 seconds to 90 seconds, more preferably from 30 seconds to 60 seconds.

<Step C>

Step C is a step of removing a portion of the film 2 by cluster ion etching of the film 2 obtained in the step B, thereby exposing at least a portion of the pattern 1. More specifically, as shown in FIG. 1(C), the cluster ions indicated by the arrows are irradiated to the film 2 (14) which is an object to be etched, and a part (upper layer portion) of the film 2 (14) is removed, thereby At least a part of the pattern 1 (12) (the upper portion of the pattern 1 in the drawing) is exposed (exposed) as shown in (D) of Fig. 1 . As described above, when the film 2 is etched by dry etching without using cluster ions, ions permeate into the pattern 1 located inside the film 2, whereby the pattern 1 is modified (hardened), and it is difficult to perform the steps described later. D removes pattern 1. On the other hand, in the case of using cluster ions, the film 2 located on the upper portion of the pattern 1 can be etched while suppressing the modification of the pattern 1.

Furthermore, it is generally preferred in this step to illuminate the cluster ion beam from the normal direction of the surface of the substrate 10.

The etching using cluster ions can be performed by using a well-known device that can illuminate a Gas Cluster Ion Beam (GCIB) (for example, an Ar gas cluster ion beam manufactured by ULVAC. PHI (with X-ray) A photoelectric spectroscopic device) or a known program is used (for example, refer to Japanese Patent Laid-Open No. Hei 4-354865, U.S. Patent No. 5,814,194, Japanese Patent Application Laid-Open No. Hei No. Hei 8-321489 (particularly after paragraph 0012), and Japanese Patent No. Table 2008-502150 (especially after paragraph 0030)).

In addition, the gas cluster ion beam refers to a large number of atoms or molecules aggregated to form a block (cluster), which is ionized and accelerated. When the high-pressure gas is ejected in a vacuum, the gas is rapidly cooled by adiabatic expansion, thereby generating a gas cluster. The gas cluster can be ionized and an electric field applied, thereby accelerating the ionized gas cluster. Gas cluster ions irradiated to the object are slightly added to the substrate. In addition, a part of the gas cluster ions are dispersed in parallel to the substrate. The surface of the substrate can be flattened by preferentially removing the irregularities formed on the substrate by a part of the gas cluster ions dispersed in parallel to the substrate surface.

As the material gas, a gas such as Ar, CO ₂ , O ₂ , N ₂ , NO, NO ₂ , NH ₃ , SF ₆ or CF ₄ or a gas obtained by mixing He for easily forming clusters of these gases can be used.

The condition for accelerating the voltage at the time of irradiating the cluster ion beam is preferably from 0.1 kV to 50 kV, more preferably from 5 kV to 30 kV, and particularly preferably from 5 kV to 20 kV, in terms of the shape of the pattern to be more excellent.

Further, as a condition of the ionization current, the obtained pattern shape is more preferably 1 nA to 400 nA, more preferably 5 nA to 200 nA, and particularly preferably 10 nA to 50 nA.

Further, as a condition of the irradiation amount, in terms of more excellent pattern shape, it is preferably 1 × 10 ⁵ ions / cm ² to 1 × 10 ³⁰ ions / cm ² , more preferably 1 × 10 ¹⁰ ions / Cm ² ~ 1 × 10 ²⁰ ions / cm ² , particularly preferably 1 × 10 ¹⁴ ions / cm ² ~ 1 × 10 ¹⁷ ions / cm ² .

In this step, as described above, a part of the film 2 is etched by cluster ions so that at least a part of the pattern 1 covered by the film 2 is exposed (exposed). By exposing at least a part of the pattern 1, the pattern 1 can be easily removed by the step D or the like described later.

Further, a part of the film 2 and the pattern 1 may be etched as needed.

<Step D>

Step D is a step performed after the step C and leaving the film 2 and removing at least a portion of the pattern 1. More specifically, by performing this step as shown in FIG. 1(E), the pattern 1 (12) can be removed and a pattern of the film 2 (14) can be formed on the substrate 10. Further, it is preferable to remove all of the pattern 1 (12) as shown in FIG. 1(E). However, the present invention is not limited to this embodiment, and the pattern 1 (12) may be made within the range in which the effects of the invention are not impaired. Part of it remains.

The method of leaving the film 2 and removing at least a part of the pattern 1 is not particularly limited, and a known method can be employed. For example, the removal treatment of the treatment liquid containing a solvent using the difference in solvent property of the film 2 and the pattern 1 with respect to a solvent can be mentioned. An etching treatment or the like which uses a difference in etching resistance between the film 2 and the pattern 1. Among them, in terms of a simple procedure and a more excellent pattern shape, a method of treating with a treatment liquid is preferred. Hereinafter, this method will be described in detail.

The type of the solvent contained in the treatment liquid to be used is not particularly limited, and an optimum solvent can be appropriately selected depending on the components of the membrane 2 and the pattern 1, and water or an organic solvent or a mixture thereof can be used. Among them, a treatment liquid containing an organic solvent is preferred in terms of the shape of the formed pattern being more excellent.

The type of the organic solvent is not particularly limited, and a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, an ether solvent, etc., which are exemplified as the organic developer described in the above step S, can be preferably used. A polar solvent and a hydrocarbon solvent.

Furthermore, the details of these solvents are as described above.

Further, as the treatment liquid, an alkaline aqueous solution exemplified as the alkaline developing solution described in the above step Z can be used.

The method of removal is not particularly limited, and for example, a method of immersing the substrate in a tank filled with the treatment liquid for a fixed period of time (dipping method) can be applied; by using surface tension to deposit the treatment liquid on the surface of the substrate and stationary for a fixed period of time Method for developing (liquid coating method); method for spraying a treatment liquid onto a surface of a substrate (spray method); a method of continuously discharging a treatment liquid onto a substrate rotating at a fixed speed while scanning a discharge nozzle at a fixed speed (Dynamic Distribution method) and so on.

In addition, the rinsing step which can be carried out in the step Z can be further carried out after the step D as needed.

By performing the steps A to D, it can be as shown in FIG. 1(E). A pattern formed by the film 2 (14) is formed on the substrate 10.

Furthermore, the manufacturing method may have steps other than the above steps A to D. For example, in the present production method, the step of removing the remaining film 2 (step E below) may be performed after step B and before step C, after step C, before step D, or after step D. By carrying out this step, the remaining film-forming components that are not attached to the pattern 1 or that have not reacted with the pattern 1 can be removed. Particularly in the case where an interaction occurs between the pattern 1 and the film forming component, by performing this step, the film forming component in the film 2 which does not interact with the pattern 1 can be removed, resulting in finer formation. picture of.

In the case of (A) to (F) of FIG. 2, when the interaction between the pattern 1 and the film formation component is sequentially formed to form an interaction film, the step is performed between the step C and the step D. A schematic cross-sectional view of the procedure of each step of the pattern forming method in the case of step E.

First, as shown in FIG. 2(A), the pattern 1 (12) is formed on the substrate 10 by performing the step A. Then, the film 2 (14) covering the pattern 1 is formed by performing the step B. At this time, an interaction occurs between the pattern 1 and the film forming component, and an interaction film 16 is formed between the pattern 1 and the film 2. Then, as shown in FIG. 2(C), the step C of irradiating the cluster ions from the direction of the arrow is performed, whereby the film 2 (14) located on the pattern 1 and a part of the interaction film 16 are removed, as shown in FIG. 2 (D). The pattern 1 is exposed (exposed) as shown. Then, by performing this step E, the remaining film 2 (the film 2 containing the film forming component which does not interact with the pattern 1) is removed as shown in FIG. 2(E), thereby being on the substrate 10 The pattern 1 and the interaction film 16 remain on the upper surface. Further, by performing the step D, the graph is as shown in FIG. 2(F). Case 1 is removed, so that the pattern containing the interaction film 16 remains on the substrate 10. By implementing the procedure, a pattern having a narrower width can be formed. Further, the width of the interactive film 16 can be appropriately adjusted depending on the film forming component to be used.

Further, in the case of (E) of FIG. 2, the remaining film 2 is completely removed. However, the present invention is not limited to this embodiment, and a part of the remaining film may remain in a range that does not impair the effects of the present invention. The form of 2. In other words, it may be a form in which at least a part of the remaining film 2 is removed.

The method of removing the remaining film 2 is not particularly limited, and it is preferred to carry out the removal using the treatment liquid of the dissolvable film 2.

The method of removing is not particularly limited, and for example, a method of immersing the substrate in a tank filled with the treatment liquid of the dissolvable film 2 for a fixed period of time (dipping method) can be applied; by using the surface tension, the treatment liquid of the dissolvable film 2 is deposited to a method of developing the surface of the substrate for a fixed period of time (liquid coating method); a method of spraying the treatment liquid of the dissolvable film 2 onto the surface of the substrate (spray method); scanning the ejection nozzle at a fixed speed while facing the fixed speed A method (dynamic distribution method) of continuously discharging the treatment liquid of the film 2 on the rotating substrate.

The type of the treatment liquid of the dissolvable film 2 is not particularly limited, and an optimum solution can be appropriately selected depending on the type of the film formation component constituting the film 2, and for example, it can be exemplified as the alkaline developer described in the above step Z. An aqueous solution or an organic solvent exemplified as an organic developing solution. Among them, water or an alcohol solvent is preferred.

The contact time of the treatment liquid of the dissolvable film 2 with the film 2 is not particularly limited, but it is preferably from 5 seconds to 180 seconds, more preferably 15 in terms of both productivity and removability. Seconds ~ 90 seconds.

Further, the rinsing step which can be carried out in the step Z can be further carried out after the first removal step as needed.

<Description of various materials>

Hereinafter, the photosensitive ray-sensitive or radiation-sensitive resin composition used in the step X and the film-forming component used in the step B will be described in detail.

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

The photosensitive ray-sensitive or radiation-sensitive resin composition contains a resin which decomposes due to the action of an acid and generates a polar group.

Further, in one embodiment, the sensitizing ray-sensitive or radiation-sensitive resin composition 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. Kind.

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 preferably has a polar group which is decomposed and desorbed by the action of an acid. The structure of the base protection.

The polar group is not particularly limited as long as it is poorly soluble or insoluble in a developing solution containing an organic solvent, and examples thereof include a phenolic hydroxyl group, a carboxyl group, and a fluorinated alcohol group (preferably a hexafluoroisopropanol group). ), sulfonic acid group, sulfonylamino group, sulfonyl sulfoximine, (alkylsulfonyl) (alkylcarbonyl) methylene, (alkylsulfonyl) (alkylcarbonyl) quinone Base, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indolylene, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)indolyl, three ( An acidic group such as an alkylcarbonyl)methylene group or a tris(alkylsulfonyl)methylene group (a group which is dissociated in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide in 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').

[Chemical 1]

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 also 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 cycloalkyl 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 having an acid-decomposable group 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 (for example, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, Second butyl, tert-butyl, etc.). 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.

[Chemical 3]

[Chemical 5]

[Chemistry 7]

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

[化8]

[Chemistry 9]

[化10]

[11]

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

[化12]

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 atom 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.

[Chemistry 13]

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.

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.

The content of the repeating unit represented by the general formula (aI) 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). %, particularly preferably 45% by mole to 70% by mole, and most preferably 50% by mole to 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. Further preferably, it has a formula (LC1-1) to a formula (LC1-21) The lactone structure represented by either of them, or a repeating unit of a sultone structure represented by any one of the following general formulas (SL1-1) to (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) and development defects become 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 formula (III), A represents an ester bond (a group represented by -COO-) or a guanamine bond (by -CONH- The base of the representation).

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, a guanamine bond, a urethane bond, Or 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.

[Chemistry 20]

[Chem. 21]

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 a repeating unit represented by the following formula (A-1).

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.

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, low defect, low line width roughness (LWR), low PEB temperature dependency, contour, and the like can be improved as a resist.

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.

[Chem. 24]

[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 group. Solution base.

In addition, the weight of the alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group The complex unit is preferably different from the repeating unit having an acid-decomposable group (i.e., preferably 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 hydroxymethyl 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 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 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.

[化28]

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. The repeating unit having an acid group is preferably 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 main chain of the resin via a linking group. a repeating unit having an acid group bonded thereto, and a polymerization initiator or a chain transfer agent having an acid group for introducing into the end of the polymer chain, 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31]

[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, an 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 mentioned.

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 hydroxymethyl 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-methyl bridge-5,8-methylnaphthyl ring Such as a tetracyclic hydrocarbon ring. In addition, the crosslinked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, such as a perhydronaphthalene ring (decahydronaphthalene ring), a perhydrohydroquinone ring, a perhydrophenanthrene ring, a perhydronaphthalene ring, a perhydroindene ring, and a total A condensed ring obtained by condensing a plurality of 5-membered cycloalkane rings, such as a hydroquinone ring or a perhydroindole ring, into a cyclopentane ring.

Preferred examples of the crosslinked cyclic hydrocarbon group include a norbornyl group, an adamantyl group, a bicyclooctyl group, and a tricyclo[5.2.1.0 ^2,6 ]nonanyl group. Preferred examples of the crosslinked cyclic hydrocarbon group include a norbornyl group and an adamantyl group.

The crosslinked cyclic hydrocarbon group 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 particularly preferably from 5 mol% to 20 mol%. %.

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 .

[repeating unit with aromatic ring]

When the photosensitive ray-sensitive or radiation-sensitive resin 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 For example, a unit having an aromatic ring represented by a repeating unit of hydroxystyrene.

The repeating unit having an aromatic ring is not particularly limited, and examples thereof include examples of the repeating unit, and examples thereof include a styrene unit, a hydroxystyrene unit, and a phenyl (meth) acrylate unit. And a hydroxyphenyl (meth) acrylate unit. More specifically, the resin (A) includes a resin containing a hydroxystyrene-based repeating unit and a hydroxystyrene-based repeating unit protected by an acid-decomposable group, and a repeating unit having the aromatic ring and A resin of a repeating unit in which a carboxylic acid moiety of acrylic acid is protected by an acid-decomposable group. Further, in particular, in the case of EUV exposure, high sensitivity is usually required, and therefore the resin (A) preferably contains a repeating unit containing a protective group which is susceptible to acid decomposition. Specific examples of the repeating unit include -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ) or -C(R) among the structures described as the group which is desorbed by the acid. ₀₁ ) (R ₀₂ ) (OR ₃₉ ) (commonly known as the structure of an acetal type protecting group).

Further, 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 included), the repeating unit (R) described in paragraph 0023 to paragraph 0102 of JP-A-2013-80002, and the like can be incorporated into the present specification. The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may further contain an acid generator not supported by the resin (A) even if the resin (A) is in a form carrying a structure corresponding to the acid generator (ie, Compound (B)) described later.

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

[化36]

In addition to the above-mentioned repeating structural unit, in order to adjust the dry etching resistance or the standard developer compatibility, the substrate adhesion, the resist profile, and further as a general characteristic of the sensitizing ray-sensitive or radiation-sensitive resin composition The resin (A) used in the photosensitive ray-sensitive or radiation-sensitive resin 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 photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention, in particular, the fine adjustment of the following properties, etc. can be achieved: (1) solubility in a coating solvent, ( 2) film forming property (glass transition point), (3) alkali developability, (4) Film thinning (hydrophobicity, alkali-soluble group selection), (5) adhesion of the unexposed portion 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 photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention, in order to adjust the dry etching resistance or the standard developer suitability of the sensitizing ray-sensitive or radiation-sensitive resin composition, The substrate adhesion, the resist profile, and further, the resolution, heat resistance, sensitivity, and the like of the general required performance of the sensitized ray-sensitive or radiation-sensitive resin composition are appropriately set, and the molar ratio of each repeating structural unit is appropriately set.

When the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is a composition for ArF exposure, the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention is used for the transparency of ArF light. The resin (A) to be used preferably has substantially no aromatic ring (specifically, the ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less. Preferably, 0 mole %, i.e., having no aromatic group, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

As a form of the resin (A) in the present invention, it may be a random type or a block. Any form of type, comb, or star. The resin (A) can be synthesized, for example, by radical polymerization, cationic polymerization, or anionic polymerization of an unsaturated monomer corresponding to each structure. Further, after polymerization using an unsaturated monomer corresponding to the precursor of each structure, a polymer reaction is carried out, whereby a target resin can also be obtained.

When the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains a hydrophobic resin (HR) to be described later, the resin (A) is more compatible with the hydrophobic resin (HR). It is preferable that the fluorine atom and the ruthenium atom are not contained (specifically, the ratio of the repeating unit having a fluorine atom or a ruthenium atom in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, and desirably 0. Moer%).

The resin (A) used in the photosensitive ray-sensitive or radiation-sensitive resin 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. As Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, and ketones such as methyl ethyl ketone and methyl isobutyl ketone, such as ethyl acetate. The solvent, a guanamine solvent such as dimethylformamide or dimethylacetamide, and further dissolves the sensitizing ray of the present invention like propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or cyclohexanone described later. Or a solvent that senses the radioactive resin composition. It is preferred to carry out polymerization using the same solvent as that used in the photosensitive ray-sensitive or radiation-sensitive resin 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, and dimethyl-2,2'-azobis(2-methylpropionate). 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 recovery 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 the solution state is a method of removing residual monomer or oligomer component by washing with water or by combining an appropriate solvent. Liquid-liquid extraction method, only extraction and removal of ultra-filtration or the like of a specific molecular weight or lower; the purification method in the solid state is by The resin solution is added dropwise to a poor solvent to solidify the resin in a poor solvent, thereby removing the residual monomer or the like by a reprecipitation method, or washing the filtered resin slurry with a poor solvent.

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

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, and nitrates. A base 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. Filtering using solvent resistance The 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 temporarily precipitated and separated, 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 be a method comprising the steps of: after the completion 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) Re-dissolving in a solvent to prepare a resin solution A (step c); thereafter, the solvent in which the resin solution A and the resin are poorly soluble or insoluble is 10 times the volume of the resin solution A (preferably 5 times or less) The volume is contacted, whereby the resin solids are precipitated (step d); the precipitated resin is separated (step e).

In addition, in order to suppress the aggregation of the resin after the preparation of the sensitizing ray-sensitive or radiation-sensitive resin composition, for example, the following steps may be added: the resin synthesized as described in JP-A-2009-037108 The solution is dissolved in a solvent to form a solution, and then the solution is heated at about 30 ° C to 90 ° C for about 30 minutes to 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.

The content of the resin (A) is preferably from 30% by mass to 99% by mass, and more preferably from 60% by mass to 95% by mass based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition.

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

Hereinafter, a specific example of the resin (A) (the composition ratio of the repeating unit is a molar ratio) will be listed, but the present invention is not limited to these specific examples. In the following, the configuration in which the structure corresponding to the acid generator described later is carried by the resin (A) is also exemplified.

[化37]

[化38]

[39]

The resin exemplified below is an example of a resin which is suitably used particularly in EUV exposure or electron beam exposure.

[化40]

[化44]

[化45]

[Chem. 46]

[化47]

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

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

The acid generator may be in the form of a low molecular compound or may be in a form incorporated into a part of the polymer. In addition, the form and composition of the low molecular compound can also be used in combination. Form into a portion of the polymer.

When the acid generator is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.

When the acid generator is in a form of being incorporated into a part of the polymer, it may be incorporated into a part of the acid-decomposable resin or may be incorporated into a resin different from the acid-decomposable resin.

In the present invention, it is preferred that the acid generator be in the form of a low molecular compound. 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).

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 another compound represented by the general formula (ZI) At least one of R ₂₀₁ to 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 cause 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), and the alkoxycarbonyl group (preferably carbon) The number is 2 to 7), the fluorenyl group (preferably having a carbon number of 2 to 12), the alkoxycarbonyloxy group (preferably having a carbon number of 2 to 7), and the alkylthio group (preferably having a carbon number of 1) ~15), alkylsulfonyl (preferably having a carbon number of 1 to 15), an alkylimidosulfonyl group (preferably having a carbon number of 2 to 15), and an aryloxysulfonyl group (preferably) a carbon number of 6 to 20), an alkylaryloxysulfonyl group (preferably having 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), a cycloalkyl alkoxyalkoxy 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.

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. One.

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.

[化53]

[化55]

[化58]

Next, the compound represented by the formula (Z1-4) will be described.

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.

l 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 (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, and an alkane. An oxycarbonyl group, an alkoxycarbonyloxy 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 Paragraph 0046, paragraph of the bulletin The cationic structure in the chemical structure and the like exemplified in the falling 0047, the paragraph 0072 to the paragraph 0077, and the paragraph 0107 to the paragraph 0110, paragraph 0135 to paragraph 0137, paragraph 0151, paragraph 0196 to paragraph 0199 of Japanese Patent Laid-Open No. 2011-53430 The cation structure or the like in the chemical structure or the like exemplified in the above.

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).

In the formula (2), Xf each 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 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 (including not only aromatic but also Examples of the aromatic group include a tetrahydropyran ring structure and 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 group, a naphthalene ring group, a phenanthrene ring group, and an anthracene ring group. Among them, from the viewpoint of absorbance at 193 nm, a naphthene ring group having a low absorbance is preferred.

Examples of the heterocyclic group include a furanyl group, a thiophene ring group, a benzofuran ring group, a benzothiophene ring group, a dibenzofuran ring group, a dibenzothiophene group, and a pyridine. Ring base. Among them, a furanyl group, a thiophene ring group, and a pyridine ring group 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.

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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 bulky 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.

[化63]

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 as the alkyl group having a substituent, an alkane having a carbon number of 1 to 5 substituted with at least one fluorine atom is preferred. The base is 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. 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 with -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.

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

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, as the acid generator, a chemical represented by the following formula (ZV) may also be mentioned. Compound.

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 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and an alkylene group having 2 to 12 carbon atoms. The number is 6~10.

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

[化68]

[化69]

[化70]

[71]

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

The content of the acid generator is preferably from 0.1% by mass to 30% by mass, more preferably from 1% by mass to 28% by mass, based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition, and more preferably 3% by mass to 25% by mass.

[hydrophobic resin]

The sensitizing 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 (in the case of immersion exposure). HR)"). 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, even when the composition is not applied to liquid immersion exposure, the hydrophobic resin can be contained for various purposes. For example, when the composition is applied to EUV exposure, it is preferable to use a hydrophobic resin in order to suppress outgassing, adjust the shape of the pattern, and the like.

The hydrophobic resin (HR) is preferably designed to be present in 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 the polar substance/nonpolar substance. Mix evenly.

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74]

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75]

[化76]

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78]

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

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 of 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 a "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. Specific examples thereof include a monocyclic structure having a carbon number of 5 or more, a bicyclic structure, a tricyclic structure, and a tetracyclic structure. 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.

[化81]

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.

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 hydroxymethyl group or a trifluoromethyl group, and 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 an organic group which does not have a "base which decomposes due to the action of an acid and generates a polar group" described in the resin (A).

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

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

[化83]

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

When the resin (HR) contains a CH ₃ partial structure in a side chain portion, and further, particularly when there is no fluorine atom or a ruthenium atom, it is represented by the general formula (II) with respect to all repeating units of the resin (HR). The content of at least one of the repeating unit and the repeating unit represented by the general formula (V) is preferably 90 mol% or more, and 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. A repeating unit or the like having an acid group bonded to the main chain may be further introduced into the end of the polymer chain by using a polymerization initiator having an acid group or a chain transfer agent during polymerization, and any of them is preferred. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a germanium atom.

The content of the repeating unit having an acid group (x) is preferably from 1 mol% to 50 mol%, more preferably from 3 mol% to 35 mol%, 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84]

As a group having a lactone structure, an acid anhydride group, or a quinone imine group (y), It is preferably a group having a lactone structure.

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

The repeating unit having a group having a lactone structure may, for example, be the same as the repeating unit having a lactone structure described in the previous section of the 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 of the group (z) which is decomposed by the action of an acid in the hydrophobic resin (HR) is the same as the repeating unit having an acid-decomposable group exemplified in the resin (A). The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a germanium atom. The content of the repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin (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).

[化86]

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 hydroxymethyl 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 two carbon atoms (C-C) which have been bonded and which is 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, the content of the fluorine atom is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 80% 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 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 from 2,000 to 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) 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 photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention. %, particularly preferably from 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. In addition, the resolution, resist shape, and resistance The molecular weight distribution (Mw/Mn, also referred to as dispersion) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2, from the viewpoints of the side wall of the etching pattern, roughness, and the like. The scope.

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. In addition, the molar ratio of the repeating unit in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion are shown in the following table.

[化89]

[化90]

[化91]

[化92]

[化93]

[化94]

[化95]

[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 (5) 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96]

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.

As the compound (N) having an imidazole structure, an imidazole, 2, 4, 5- Triphenylimidazole, benzimidazole, 2-phenylbenzimidazole, and the like. Examples of the compound (N) having a diazabicyclo structure include 1,4-diazabicyclo[2.2.2]octane and 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 the 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).

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 described in WO2011/158687A1<0416>~<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 sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may contain a basic compound (N) or may not contain a basic compound (N), and when it contains a basic compound (N), it may be sensitized or sensitized. 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 based on the solid content of the radiation-based resin composition.

The ratio of use of the acid generator to the basic compound (N) in the sensitizing ray-sensitive or radiation-sensitive resin composition is preferably an acid generator/basic compound (mol ratio) = 2.5 to 300. That is, in terms of sensitivity and resolution, Mohr is preferably 2.5 or more. From the viewpoint of suppressing a decrease in the resolution caused by the coarseness of the resist pattern up to the post-exposure heat treatment over time, the molar ratio is preferably 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 -.

Furthermore, -NH- is equivalent to an acid produced by irradiation with actinic rays or radiation. Sex functional group.

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98]

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 sensitized ray-sensitive or radiation-sensitive resin composition of the present invention may also contain A compound having a nitrogen atom and having a group which is desorbed by the action of an acid (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. Particularly preferred are urethane groups and half amine acetal groups.

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.

Of R _b the same meaning as in the general formula (d-1) in a R _b, preferred embodiments 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 R _a (the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group may be substituted by the group) may be enumerated and targeted. The preferred examples of R _{b are} the same.

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, 1,4,5,6-tetrahydropyrimidine, and 1 , 2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 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, anthracene a base of a heterocyclic compound such as ruthenium, porphyrin, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane; a chain of a chain 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 phenyl 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 general formula (6) can be opened according to Japanese patents It is synthesized by the publication of Japanese Patent Laid-Open No. 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 from 0.001% by mass to 20% based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition. % is more preferably 0.001% by mass to 10% by mass, still more preferably 0.01% by mass to 5% by mass.

(4) strontium salt

Further, the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may contain a cerium salt as a basic compound. Examples of the onium salt include an onium salt represented by the following formula (6A) or formula (6B). The bismuth salt is expected to control the diffusion of the acid generated in the resist composition due to the relationship with the acid strength of the photoacid generator generally used in the resist composition.

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 examples of the phosphonium cation and the phosphonium cation, the above may also be preferably exemplified. The phosphonium cation structure of the formula (ZI) in the compound (B) or the fluorene structure in the formula (ZII).

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

When the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a cerium salt represented by the general formula (6A) or the general formula (6B), the solid content of the sensitized ray-sensitive or radiation-sensitive resin composition is used. The content of the material is usually from 0.01% by mass to 10% by mass, preferably from 0.1% by mass to 5% by mass.

(5) Betaine compounds

Further, the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention can also preferably use a compound contained in the formula (I) of JP-A-2012-189977, Japanese Patent Laid-Open Publication No. 2013-6827 The compound represented by the formula (I), the compound represented by the formula (I) of JP-A-2013-8020, and the formula (I) of JP-A-2012-252124 of A compound having a sulfonium salt structure and an acid anion structure in one molecule (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, an alkyl pyruvate or a methyl 2-hydroxyisobutyrate.

Specific examples of such a solvent include those described in the specification of 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 kinds of a surfactant (a fluorine-based surfactant, a lanthanoid surfactant, and a surfactant having 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 lanthanum-based surfactant include the surfactants described in <0276> of the specification of the US Patent Application Publication No. 2008/0248425, for example, Eftop EF301 and EF303. (New Akita Chemicals Co., Ltd.), Fluorad FC430, 431, 4430 (manufactured by Sumitomo 3M), Megafac F171, F173, F176, F189, F113, F110 , F177, F120, R08 (made by Di Love (DIC) (share)), Surflon S-382, SC101, 102, 103, 104, 105, 106, KH-20 (made by Asahi Glass Co., Ltd.) , Tory (Troysol) S-366 (Troy Chemical (Troy Chemical) (manufactured by Troy Chemical), 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 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX -204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (manufactured by Neos). 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).

In addition, in the present invention, the US Patent Application Publication No. A surfactant other than the fluorine-based surfactant and/or the lanthanoid surfactant described in <0280> of the specification of 2008/0248425.

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 sensitizing ray-sensitive or radiation-sensitive resin 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 In the bulletin, etc. Recorded.

Further, the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention preferably has a low water content. Specifically, the water content is preferably 2.5% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.3% by mass or less based on the total weight of the composition.

<film forming component (spacer agent)>

Hereinafter, the film formation component used in the step B will be described in detail.

(film forming component)

The film forming component is a material used to constitute the film 2, and the kind thereof is not particularly limited, and it is generally preferred to use an organic substance.

As the organic substance, any of a low molecular compound and a high molecular compound can be used, and a polymer compound (a compound having a repeating unit) is more preferable. Further, the low molecular compound is a compound having a molecular weight of less than 1,000, and the polymer compound is a compound having a molecular weight of 1,000 or more.

Further, the molecular weight of the organic substance is not particularly limited, but is preferably 1,000 or more, and more preferably 10,000 or more.

The degree of dispersion (Mw/Mn) of the polymer compound is not particularly limited, but is preferably from 1.0 to 3.0, more preferably from 1.0 to 2.0, in terms of the shape of the pattern to be formed.

The Mw (weight average molecular weight) of the polymer compound is not particularly limited, but is preferably from 1,000 to 60,000, more preferably from 3,000 to 25,000, in terms of the shape of the pattern to be formed.

In addition, the film forming component may use a component that can form an interaction with the pattern 1, Not any of the ingredients. Further, the film forming component itself may have crosslinkability, and the film forming components may react with each other to form the film 2 having a crosslinked structure.

Among them, in terms of forming an interaction film as shown in Fig. 2, the film formation component is preferably a component (compound) which can form an interaction with the pattern 1. In particular, in the case where the photosensitive ray-sensitive or radiation-sensitive resin composition used in the formation of the pattern 1 contains a resin which decomposes due to the action of an acid and generates a polar group, it is preferably used in the polar group. Membrane-forming components that interact (eg, chemical bonds, electrostatic interactions, hydrogen bonds, dipole interactions, coordination bonds, etc.).

The film forming component which can form an interaction as described above is, for example, at least one selected from the group consisting of a phosphonium salt compound, a nitrogen-containing compound, and a phosphorus-based compound.

These compounds may be in the form of a low molecular compound or in the form of a polymer compound, and are 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.

Further, as the cation in the onium salt structure, a positive charge is also included in the hetero atom of the heteroaromatic ring. 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.

As the onium salt compound, in terms of the effect of the present invention being more excellent, It may also be a polyvalent sulfonium salt compound having two or more cesium ion atoms in one molecule. 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, a phosphonium salt, an ammonium salt, and a phosphonium 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 ₅ ) 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.

[化106]

[107]

[化108]

[化109]

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

Specific examples of the onium salt structure are exemplified below.

[化112]

[化113]

[化114]

[化115]

[116]

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

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.

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 carbons contained in the aromatic hydrocarbon group is not particularly limited, but the present invention The viewpoint of the more excellent effect 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.

[化118]

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 bonded nitrogen atoms.

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.

Examples of the n-valent aliphatic cyclic hydrocarbon group having 3 to 30 carbon atoms represented by the above R ⁶ include a ring 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 hydrocarbon group.

The n-valent aromatic hydrocarbon group having 6 to 14 carbon atoms represented by the above R ⁶ may, for example, be an aromatic group having 6 to 14 carbon atoms 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.

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. Amines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-decylamine, di-n-decylamine, cyclohexylmethylamine, Di(cyclo)alkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octane Amine, tri-n-decylamine, tri-n-decylamine, cyclohexyldimethylamine, A Tri(cyclo)alkylamines such as dicyclohexylamine and tricyclohexylamine; substituted alkylamines 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- Third butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, An aromatic amine such as 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'-diaminobenzophenone, 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 a nitrogen-containing aromatic heterocyclic compound and a nitrogen-containing aliphatic heterocyclic compound.

Examples of the nitrogen-containing aromatic heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, and 1-benzyl group. Imidazoles such as 2-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 - Pyridines such as 8-oxyquinoline, acridine, 2,2':6', 2"-terpyridine.

Examples of the nitrogen-containing aliphatic heterocyclic compound include piperazines such as piperazine and 1-(2-hydroxyethyl)piperazine; pyrazine, pyrazole, pyridazine, quinazoline, anthracene, pyrrolidine, and the like. Proline, piperidine, piperidine ethanol, 3-piperidinyl-1,2-propanediol, morpholine, 4-methylmorpholine, 1-(4-morpholinyl)ethanol, 4-ethylidene Porphyrin, 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-(Tertoxycarbonyl)-2-pyrrolidinemethanol, N-tert-butoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonylpyrrolidine, N-third Butoxycarbonylpiperazine, N,N-di-t-butoxycarbonyl-1-adamantylamine, N,N-di-t-butoxycarbonyl-N-methyl-1-adamantyl 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- Third butoxycarbonyl-1,8-diaminooctane, N,N'-di-third Oxycarbonyl-1,9-diaminodecane, N,N'-di-t-butoxycarbonyl-1,10-diaminodecane, N,N'-di-t-butoxy Carbonyl-1,12-diaminododecane, N,N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, N-tert-butoxycarbonylbenzene An N-tert-butoxycarbonyl-containing amine-based compound such as imidazole, N-t-butoxycarbonyl-2-methylbenzimidazole, N-t-butoxycarbonyl-2-phenylbenzimidazole; Formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propylamine, Benzoamide, pyrrolidone, N-methylpyrrolidone, N-ethinyl-1-adamantylamine, tris(2-hydroxyethyl) isocyanurate, and the like.

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.

A suitable form of the nitrogen-containing compound is preferably a nitrogen-containing compound (multivalent nitrogen-containing compound) containing a plurality of (two or more) nitrogen atoms. 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.

[化120]

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. Alkyl group It may be a straight chain, may also be a branch, 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 an alkyl group, a cycloalkyl group, and an 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 the effect of the present invention is more excellent. From the viewpoint, 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.

[化122]

[化123]

(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 compound may contain at least one phosphorus atom, and may contain Multiple (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.

[化125]

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 sulfonium salt structure is as described above, and the definitions of cations and anions are also the same. this.

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 extended 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.

A suitable form of the repeating unit represented by the formula (5-1) is a repeating unit represented by the formula (5-2).

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132]

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134]

[化135]

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 film forming component may be a component other than the film forming component capable of forming the interaction.

For example, a known resin can be used, and examples thereof include a resin having a repeating unit exemplified in the resin (A). Further, a plurality of the repeating units exemplified in the above (A) may be contained in the resin.

The resin may or may not contain a repeating unit having an acid-decomposable group.

Moreover, as one of the preferable forms of the resin, a resin having a reactive group which can react with a crosslinkable group contained in a crosslinking component to be described later is preferable. The type of the reactive group is not particularly limited, and an optimum group can be appropriately selected depending on the kind of the crosslinking group. Among them, an -OH group is preferred. Examples of the -OH group include a phenolic hydroxyl group (an -OH group substituted on an aromatic group) and an alcoholic hydroxyl group (not a phenolic hydroxyl group). Thereby, it is expected to improve the crosslinkability with the crosslinking component mentioned later.

As the film forming component, for example, a crosslinking component having a crosslinkable group can be preferably used. The mechanical strength of the formed film 2 is increased by using a crosslinking component. It is especially preferred to use the form of the resin and the crosslinking component in combination.

The type of the crosslinking component is not particularly limited, and a known crosslinking component can be used. The type of the crosslinkable group contained in the crosslinking component is not particularly limited, and examples thereof include a hydroxyl group-containing functional group (for example, methylol group, dimethylolaminomethyl group, dihydroxyethylaminomethyl group). a functional group containing a nitrogen atom (for example, an imido group, an oxazoline group, an imidazolium group, a dimethylaminomethyl group, a diethylaminomethyl group, etc.), an ether group-containing functional group ( For example, a chain ether group such as a methoxymethyl group, an ethoxymethyl group, a benzyloxymethyl group, an ethoxymethyl group, a benzhydryloxymethyl group or a morpholinyl group, or an oxetanyl group A cyclic ether group such as a glycidyl ether group or a glycidyl ester group, or a functional group containing a polymerizable carbon-carbon double bond (for example, (meth)acrylonitrile group or vinyl group).

It is preferred to contain two or more of the crosslinkable groups in the crosslinking component, and more preferably from 2 to 10.

Further, as the crosslinking component, two or more rings may be suitably included. An ether group-containing compound, a compound containing two or more (meth)acryl fluorenyl groups, or a compound containing a group represented by the following formula (3).

The crosslinking component may be used alone or in combination of two or more.

In the formula (3), R ⁴ and R ⁵ are each a hydrogen atom or represented by the following formula (4), and at least one of R ⁴ and R ⁵ is represented by the following formula (4);

In the formula (4), R ⁶ and R ⁷ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, or a carbon in which R ⁶ and R ⁷ are bonded to each other. The number is a ring of 2 to 10, and R ⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In addition, as a compound containing two or more (meth) acryloyl fluorenyl groups, the compound represented by the following formula (1) is mentioned suitably.

[化138]

In the formula (1), A and D represent a hydrocarbon group having 1 to 10 carbon atoms, and B represents a single bond, an ester, and -O-. R represents hydrogen or a methyl group, and may be the same or different. m and n are integers from 1 to 5, and m+n=2 to 8. However, when the carbon number of A or D is 1, m or n is 1 to 3, respectively.

Further, from the viewpoint of controlling the crosslinking reaction, a base may be further used as the film-forming component. The type of the base is not particularly limited, and examples thereof include the basic compound which may be contained in the sensitizing ray-sensitive or radiation-sensitive resin composition.

Further, a surfactant may be further used as the film forming component. The type of the surfactant is not particularly limited, and examples thereof include the surfactant which may be contained in the sensitizing ray-sensitive or radiation-sensitive resin composition.

As described above, one of the suitable forms of the film-forming component preferably contains a resin, more preferably a resin and a crosslinking component, and particularly preferably a form containing a resin and a crosslinking component, and an alkali and/or a surfactant.

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.).

Further, the pattern forming method of the present invention can also be suitably used for a guide pattern in Directed Self-Assembly (DSA) (for example, refer to "ACS Nano" Vol. 4 No. 8 4815 Page - 4823).

[Examples]

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

(Synthesis Example 1)

Under a nitrogen gas stream, 40 g of a propylene glycol monomethyl ether acetate and a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether were placed in a three-necked flask, and heated to 80 ° C (solvent 1). The monomer corresponding to the repeating unit described below was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate and 6/4 (mass ratio) of propylene glycol monomethyl ether at a molar ratio of 30/10/60. While preparing a 22% by mass of a monomer solution (400 g). Furthermore, 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.

Resin (P-2) to resin (P-9) was synthesized in the same manner as in Synthesis Example 1 except that the monomer corresponding to each repeating unit was used in such a manner as to become a desired composition ratio (mole ratio). And a hydrophobic resin (N-1) to a hydrophobic resin (N-3).

[化139]

(Photosensitized ray-sensitive or radiation-sensitive resin composition (resist composition))

The components shown in the following Table 4 were dissolved in the solvent shown in the table to make the total solid content concentration 3.5% by mass, and each was filtered using a polyethylene filter having a pore diameter of 0.05 μm. A resist composition Ar-1 to a resist composition Ar-14 was prepared.

[resin]

The composition ratio (molar ratio), weight average molecular weight, and degree of dispersion of the resin used in Table 4 are shown below.

[化140]

[acid generator]

The structural formula of the acid generator is shown below.

[化141]

[alkaline compound]

The structural formula of the basic compound is shown below.

[化142]

[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143]

The abbreviations in Table 4 are as follows.

[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 (made 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

<Examples and Comparative Examples>

<Formation of pattern: dry exposure>

The organic anti-reflective film formation ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied onto a tantalum wafer (hereinafter also referred to as "wafer"), and baked at 205 ° C for 60 seconds to form a film thickness of 86 nm. Anti-reflective film. The resist composition (any of Ar-1 to Ar-14) was applied thereon, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 75 nm (film 1). .

Then, an ArF凖 molecular laser scanner (ASML) was manufactured by a 1:1 line and space mask with a line width of 72 nm; PAS5500, with a numerical aperture of 0.75, Dipole, The resist film was exposed by an outer sigma of 0.89 and an inner sigma of 0.65.

Thereafter, the exposed resist film was heated on a hot plate at 95 ° C for 60 seconds, and then cooled to room temperature. Then, development was carried out by coating the first developing solution described in the following Tables 6 and 7 for 20 seconds. For the examples of the first eluent described in Tables 6 and 7, the following Table 6 and Table are used. The first eluent liquid coating 30 described in 7 The rinsing is performed in seconds to form the pattern 1.

The spacer forming compositions described in Tables 6 and 7 are applied to the respective patterns 1 obtained as described above, and the temperatures (° C.) and the baking columns in Tables 6 and 7 are described. An example of time (seconds) is baked at this temperature and time to form a film 2 having a film thickness of 200 nm (thickness of the surface of the antireflection film as a reference surface).

Then, the obtained film 2 was etched by the following apparatus and conditions until the pattern 1 was exposed.

GCIB: Ar gas cluster ion beam (with X-ray photoelectric spectrometer) manufactured by AGVAC.

Conditions: Acceleration voltage 5kV, ionization current 20nA, irradiation area 5.0mm × 5.0mm, rotation with Zalar

Further, regarding Conditions 1 to 4 in Comparative Examples 1 to 5, the film 2 was etched by the following apparatus and the conditions described in Table 5. Further, the etching treatment of Conditions 1 to 4 is not a form in which cluster ions are used.

As the etching device, an Etch Centura DPS having a high frequency plasma source (DPS) manufactured by Applied Materials, Inc. was used. The DPS chamber includes a vacuum chamber, a high-frequency power source (source power source) for generating plasma at an upper portion of the vacuum chamber, and a high-frequency power source for anisotropically irradiating ions to the substrate at a lower portion of the wafer. (bias power supply).

The frequency of the upper high-frequency power source (source power source) is 2 MHz, and the frequency of the lower high-frequency power source (bias power source) is set to 13.56 MHz. In addition, the wafer cooling temperature at the time of etching was 20 °C.

The ICP power and bias power in the table indicate the power input to the source power source and the bias power source, respectively, and the pressure is the process pressure at the time of etching. Further, the gas flow rate indicates the flow rate of the process gas flowing during the etching, and is controlled by a mass flow controller. The processing time indicates the time at which the etching process is performed.

The tantalum wafer subjected to the above treatment was washed with the first removal liquid for 20 seconds. An example of the second eluent is described in Tables 6 and 7, after the rinsing was performed using the second eluent, and then the wafer was rotated at 2000 rpm for 30 seconds to remove the remaining film 2. This process is equivalent to the step E described above.

Further, examples of the second removal liquid described in Tables 6 and 7 are developed using the second removal liquid for 20 seconds, and the third rinse solution is described in Tables 6 and 7, and the third rinse is used. After the liquid was rinsed, the wafer was rotated at 4000 rpm for 30 seconds, thereby removing the pattern 1 to obtain a 1:1 line and space resist pattern having a line width of 36 nm. This processing is equivalent to the step D described above.

<Formation of pattern: immersion exposure>

In addition to changing the method of forming the pattern 1 to the following method (liquid immersion exposure method) Other than this, a resist pattern was obtained in the same procedure as the <form formation: dry exposure>. Further, a resist pattern having a line width of the obtained resist pattern of 1:1 line and space of 22 nm was obtained.

(liquid immersion exposure method)

The organic antireflection film formation was applied to a tantalum wafer by ARC29SR (manufactured by Nissan Chemical Co., Ltd.), and baked at 205 ° C for 60 seconds to form an antireflection film having a film thickness of 98 nm. The resist composition (any of Ar-1 to Ar-14) was applied thereon, and baked at 90 ° C for 60 seconds to form a resist film having a film thickness of 60 nm (film 1). .

Then, an ArF凖 molecular laser immersion scanner (XT1700i manufactured by Esmol), with a numerical aperture of 1.20, dipole, was used by a 1:1 line with a line width of 44 nm and a 6% halftone mask of the space pattern. The outer sigma was 0.981 and the inner sigma was 0.895, Y biased to expose the resist film. The liquid immersion liquid uses ultrapure water. Thereafter, the exposed resist film was heated at 95 ° C for 60 seconds, and then cooled to room temperature. Then, development was carried out by coating the first developing solution described in the following Tables 6 and 7 for 20 seconds. For the examples of the first eluent described in Tables 6 and 7, the following Table 6 and Table are used. The first eluent liquid described in 7 was rinsed for 30 seconds to form a pattern 1.

<pattern bridge defect evaluation>

The obtained pattern (spacer pattern) was observed by a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.), and the following three-stage evaluation was performed.

A: No bridge is observed between the patterns.

B: A slight observation of the bridge between the patterns

C: The situation of bridging everywhere between patterns

<Line width roughness (LWR) evaluation of pattern>

In the obtained pattern, the line pattern was observed by a scanning electron microscope (S9280 manufactured by Hitachi, Ltd.), and the distance from the reference line of the edge was measured at 50 points in the range of 2 μm in the longitudinal direction of the line pattern. The standard deviation is calculated as 3σ. A smaller value indicates a better performance.

In addition, in the following Tables 6 and 7, when the spacer agent is S-1 to S-8 and S-15, the "Mw" in the "spacer" column indicates the molecular weight (the mass of one molecule). In the case where the spacer agent is S-9 to S-14 and S-16, "Mw" in the "spacer" column indicates the weight average molecular weight.

The abbreviations in Tables 6 and 7 are as follows.

TMAH: aqueous solution of tetramethylammonium hydroxide (concentration: 2.38 mass%)

MIBC: 4-methyl-2-pentanol

PGMEA: propylene glycol monomethyl ether acetate

EL: ethyl lactate

MAK: 2-heptanone

Organic solvent A: A solvent obtained by mixing a spacer S-1 described later with respect to butyl acetate at a ratio of 2% by mass.

[spacer agent]

The spacer agent used in Table 6 and Table 7 is shown below.

[化144]

Further, in Tables 6 and 7, a plurality of different molecular weights were used for the above S-10.

In Tables 6 and 7, the "ArF dry" column indicates the evaluation of the pattern formed by the formation of the pattern: dry exposure, and the "ArF liquid immersion" column indicates the formation of the pattern by the liquid immersion: Exposure > Evaluation of the formed pattern.

As shown in Table 6 and Table 7, the pattern forming method according to the present invention can be obtained. A pattern with fewer defects. When it is confirmed that the molecular weight of the film-forming component is 1000 or more, a more excellent effect can be obtained. In addition, as a solvent in the composition for forming a spacer, LWR is more excellent in a system having a small content of water (a system using only an organic solvent as a solvent).

On the other hand, in Comparative Example 1 to Comparative Example 5 in which etching using cluster ions was not performed, the desired effect was not obtained.

Although the embodiment has been described above, the present invention is not limited to the embodiments. For example, the pattern can be formed by the following forms (form X and form Y).

Form X: a form in which a negative-type development is performed by adding a nitrogen-containing basic compound such as trioctylamine in an amount of about 1% by mass to the butyl acetate developing solution used in the step A to the second embodiment.

Form Y (form of EUV exposure): In the examples, an exposure using an ArF凖 molecular laser is converted into an EUV exposure form, and further used as a resin in a resist composition, which is used as the “EUV in particular”. The form of the resin described in the case of exposure or electron beam exposure.

(Preparation of a composition for forming a spacer)

The components shown in the following Table 8 were dissolved in the solvent shown in the table to make the total solid content concentration 4% by mass, and each was filtered by a filter having a pore diameter of 0.1 μm, and the interval was prepared. A composition for forming a substance (treatment agent 1 to treatment agent 23).

[resin]

The composition ratio (mole ratio), weight average molecular weight, and dispersity of the resin used in Table 8 are shown below.

V-13: Polyethylene acetal resin (manufactured by Sekisui Chemical Co., Ltd., trade name "ESREC KW-3")

V-15: Copolymer of N-vinylpyrrolidone and N-vinylimidazole (manufactured by BASF Corporation under the trade name "Sokalan HP56 K")

[化148]

[Crosslinking ingredient 1]

X-1: ethylene glycol diglycidyl ether (2 epoxy groups, trade name: Epolight 40E, manufactured by Kyoeisha Chemical Co., Ltd.)

X-2: Trimethylolethane triglycidyl ether (3 epoxy groups, trade name: Ai Epolight 100MF, manufactured by Kyoeisha Chemical Co., Ltd.)

X-3: dimethylolpropane diglycidyl ether (2 epoxy groups, trade name: Epolight 1500NP, manufactured by Kyoeisha Chemical Co., Ltd.)

X-4: pentaerythritol tetraglycidyl ether (4 epoxy groups, trade name: Denacol EX-411, manufactured by Nagase ChemteX)

X-5: dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether (6 oxetanyl)

X-6: NIKALAC MX-750 (manufactured by Nippon Carbide Co., Ltd., trade name)

X-7: dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether

X-9: Tetra(hydroxymethyl) glycoluril (manufactured by Cytec Co., Ltd., trade name "Cymel" 1172)

[Crosslinking ingredient 2]

XII-1: methoxymethylated melamine resin (trade name: Cymel) 300, manufactured by Japan's Sytecs (sytecs)

XII-2: methoxymethylated melamine resin (trade name: Cymel 325, manufactured by Sitkus, Japan)

[additive]

AD-1: Triethylamine

[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)

W-5: PlySurf A210G (Manufactured by First Industrial Pharmaceuticals Co., Ltd.) (phosphate ester)

The composition for forming a spacer is used, and the composition for forming a spacer (the processing agent 1 to the treatment agent 23, respectively) is used, and the baking temperature and time described in Table 8 are changed, and In the same manner as in Example 1, patterning was carried out, and as a result, a pattern was formed in the same manner as in Example 1 in any form.

10‧‧‧Substrate

12‧‧‧ Pattern 1

14‧‧‧ membrane 2

Claims (11)

A pattern forming method comprising: step A, forming a pattern 1 containing an organic substance on a substrate; step B, forming a film 2 covering the pattern 1; and step C, etching the film 2 by cluster ions A portion of the film 2 is removed to expose at least a portion of the pattern 1. The pattern forming method according to claim 1, wherein after the step C, the step D of residing the film 2 and removing at least a portion of the pattern 1 is further included. The pattern forming method according to the first or second aspect of the invention, wherein the step A includes a step of forming a film 1 on the substrate using a sensitizing ray-sensitive or radiation-sensitive resin composition, The step of irradiating the film 1 with actinic rays or radiation, and developing the film 1 after the irradiation to form the pattern 1 is performed. The pattern forming method according to claim 3, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition is a composition containing a resin having an increased polarity due to an action of an acid. The pattern forming method according to claim 3, wherein the development of the film 1 is carried out using an aqueous alkaline solution. The pattern forming method according to claim 4, wherein the development of the film 1 is carried out using an aqueous alkaline solution. The pattern forming method according to any one of claims 1 to 6, wherein the step B contains a composition used for forming the film 2 a step of coating on the pattern 1. The pattern forming method according to the seventh aspect of the invention, wherein the composition used for forming the film 2 is a composition containing a film forming component and an organic solvent. The pattern forming method according to claim 8, wherein the organic solvent contains at least one of an alcohol solvent and an ether solvent. The pattern forming method according to any one of claims 2 to 6, wherein the step D includes a step of removing at least a portion of the pattern 1 by a treatment liquid containing an organic solvent. A method of producing an electronic component, comprising the pattern forming method according to any one of claims 1 to 6.