JP2015132811A - Pattern formation method, and method for producing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern formation method in which defects are less likely to occur, and a method for producing an electronic device.SOLUTION: A pattern formation method involves: a step (A) for forming a pattern (1), which includes an organic substance, on a substrate; a step (B) for forming a film (2) covering the pattern (1); and a step (C) for exposing at least a portion of the pattern (1) by removing a portion of the film (2) by etching the film (2) with cluster ions.

Description

  The present invention relates to a pattern forming method and an electronic device manufacturing method applicable to a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and further to a photolithographic lithography process. In particular, the present invention relates to a pattern forming method and an electronic device manufacturing method suitable for exposure in an ArF exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source.

Since the resist for KrF excimer laser (248 nm), a pattern formation method using chemical amplification has been used to compensate for the sensitivity reduction due to light absorption.
To reduce the size of semiconductor elements, the exposure light source has become shorter in wavelength and the projection lens has a higher numerical aperture (NA). ing. As a technique for further increasing the resolving power, a method of filling a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) between the projection lens and the sample (that is, an immersion method) has been proposed. In addition, EUV lithography in which exposure is performed with ultraviolet light having a shorter wavelength (13.5 nm) has also been proposed.

Recently, in addition to shortening the wavelength of the exposure light source and increasing the numerical aperture (high NA) of the projection lens, various processes (processes) have been devised, such as various physical and chemical effects on the formed resist pattern. Many attempts have been made to obtain a fine pattern size exceeding the optical resolution limit by performing the processing.
As one of such attempts, for example, there is a pattern forming method as described in Patent Document 1. More specifically, in this pattern forming method, (1) a step of forming a resist pattern on a substrate, (2) a step of forming a cross-linked layer so as to cover the resist pattern, (3) a formed cross-linked layer (4) removing the resist pattern by dry etching, leaving the cross-linked layer formed on the lateral portion of the resist pattern, and leaving the remaining cross-linked layer as a final A mask pattern.

Special table 2010-534306 gazette

  However, in this technique, the dry etching of (3) above is particularly necessary for removing the cross-linked layer, while dry etching may cause unintended modification (curing) of the resist pattern on the substrate, etc. For example, there is a concern that removal of the resist pattern does not proceed sufficiently and problems such as bridge defects occur. In order to reduce such concerns and apply the above technique to actual mass production, further improvements were necessary.

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

As a result of intensive studies on the problems of the prior art, the present inventors have found that the above-described problems can be solved by performing an etching process with cluster ions.
That is, it has been found that the above object can be achieved by the following configuration.

(1) Step A of forming a pattern 1 containing an organic substance on a substrate;
A step B of forming a film 2 covering the pattern 1;
A pattern forming method comprising: etching the film 2 with cluster ions to remove a part of the film 2 and exposing at least a part of the pattern 1.
(2) The pattern forming method according to (1), further including a step D of removing at least a part of the pattern 1 while leaving the film 2 after the step C.
(3) Step A includes a step of forming film 1 on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition, a step of irradiating film 1 with actinic rays or radiation, and a post-irradiation step. The pattern formation method as described in (1) or (2) including the process of developing the film | membrane 1 and forming the pattern 1. FIG.
(4) The pattern forming method according to (3), wherein the actinic 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 performed using an alkaline aqueous solution.
(6) The pattern formation method in any one of (1)-(5) in which the process B includes the process of apply | coating the composition used for formation of the film | membrane 2 on the pattern 1. FIG.
(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 includes at least one of an alcohol solvent and an ether solvent.
(9) The pattern formation method in any one of (2)-(8) in which the process D includes the process of removing at least one part of the pattern 1 with the process liquid containing an organic solvent.
(10) A method for manufacturing an electronic device, including the pattern forming method according to any one of (1) to (9).

  ADVANTAGE OF THE INVENTION According to this invention, the pattern formation method which a defect does not produce easily can be provided.

It is typical sectional drawing which shows the procedure of each process of one embodiment of the pattern formation method of this invention in order. It is typical sectional drawing which shows the procedure of each process of the other embodiment of the pattern formation method of this invention in order.

Hereinafter, modes for carrying out the present invention will be described.
In addition, in the description of a group (atomic group) in this specification, the description which does not describe substitution and non-substitution means a group (atomic group) having a substituent together with a group (atomic group) having no substituent. ). For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “active light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.

One of the features of the present invention is that an etching process using cluster ions is performed. The mechanism of the present invention is presumed as follows.
As described above, Patent Document 1 adopts a method of removing a part of the crosslinked layer by dry etching. However, during this dry etching, ions pass through the cross-linked layer and reach the resist pattern disposed below the cross-linked layer, so that the modification (for example, carbonization) of the resist pattern proceeds. As a result, the resist pattern cannot be removed by a removal method using a solvent or the like, and a desired pattern cannot be obtained. On the other hand, when etching with cluster ions is performed, it is difficult for the cluster ions irradiated onto the film 2 to be etched to reach the pattern 1 through the film 2 due to its properties. The denaturation of the pattern 1 is suppressed and a desired pattern is obtained.

The pattern forming method of the present invention includes at least the following three steps.
Process A: Process 1 for forming pattern 1 containing organic substance on substrate Process B: Process 2 for forming film 2 covering pattern 1 Process C: Etching film 2 with cluster ions to remove a part of film 2 Step of exposing at least part of pattern 1 Note that the steps A to C are preferably performed in the order of step A to step C.
Moreover, it is preferable that the following process D is further included after the process C other than the said process A-process C.
Step D: Step of removing at least part of the pattern 1 while leaving the film 2 after the step C. FIG. 1 is a schematic cross-sectional view sequentially showing the procedure of each step of one embodiment of the pattern forming method of the present invention. FIG. The procedure of each step of the pattern forming method will be described in detail below with reference to FIG. In addition, in FIG. 1, one embodiment of the pattern formation method containing the said process A-process D is explained in full detail.

<Process A>
Step A is a step of forming a pattern 1 containing an organic substance on a substrate. By performing this step, a pattern 1 (12) is formed on the substrate 10 as shown in FIG. In FIG. 1A, the pattern 1 (12) is arranged in a stripe shape, but is not limited to this mode and can take various pattern shapes.
As long as the pattern 1 containing an organic substance is formed in the specific procedure of the process A, the pattern formation method and the material used are not specifically limited. For example, (1) pattern 1 is formed by pattern exposure of the film 1 obtained using the actinic ray-sensitive or radiation-sensitive resin composition, and development with an appropriate developer, and (2) so-called nanoimprint. Pattern 1 is formed by technology (for example, “Basics of Nanoimprint and Technology Development / Application Deployment-Nanoimprint Substrate Technology and Latest Technology Deployment”) edited by Yoshihiko Hirai, published by Frontier Publishing Co., Ltd.), (3) so-called Pattern 1 is formed by pattern formation by self-organization (Directed Self Assembly: DSA) (see, for example, Japanese Patent Laid-Open No. 2008-036491, Proceedings of SPIE, Vol. 7637, No. 76370G-1, etc.) Conceivable. In addition, this process may further include the process of improving the surface roughness of a pattern as described in Unexamined-Japanese-Patent No. 2004-235468 and Unexamined-Japanese-Patent No. 2005-19969, for example.
Among these, the film 1 obtained by using the above-mentioned (1) actinic ray-sensitive or radiation-sensitive resin composition is subjected to pattern exposure in that the shape of the resulting pattern 1 can be more easily controlled, and an appropriate developer. It is preferable to form the pattern 1 by performing a development process. Hereinafter, this method will be described in detail.

More specifically, the method (1) includes a step of forming the film 1 on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also simply referred to as “composition”); It is preferable that they are a step of irradiating the obtained film 1 with actinic rays or radiation and a step of developing the irradiated film 1 to form the pattern 1. Hereinafter, this process will be described in detail by dividing it into the following three procedures.
(Step X) Step of forming film 1 on the substrate using actinic ray-sensitive or radiation-sensitive resin composition (Step Y) Step of irradiating film 1 with actinic rays or radiation (Step Z) Film 1 Step of developing pattern 1 to develop pattern 1 The actinic ray-sensitive or radiation-sensitive resin composition used in step X will be described in detail later. Further, the film 1 formed in the process A (process X, process Y, and process Z) is hereinafter simply referred to as “film”.

(Process X)
Process X is a process of forming a film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition.
The method for forming a film on the substrate using the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, and a known method can be adopted. Especially, the method of apply | coating an actinic-light sensitive or radiation sensitive resin composition on a board | substrate from the point which adjustment of the thickness of a film | membrane is easier is mentioned.
The application method is not particularly limited, and a known method can be adopted. Among these, spin coating is preferably used in the semiconductor manufacturing field.

The substrate on which the film is formed is not particularly limited, and an inorganic substrate such as silicon, SiN, SiO ₂ or SiN, a coated inorganic substrate such as SOG, a semiconductor manufacturing process such as an IC, a circuit such as a liquid crystal or a thermal head A substrate generally used in the substrate manufacturing process, and also in other photofabrication lithography processes can be used. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the step Y described later.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after step Y and before step Z.
The heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB. The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like. The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

The receding contact angle of the film (resist film) formed using the actinic ray-sensitive or radiation-sensitive resin composition is preferably 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. It is suitable when it exposes via, It is more preferable that it is 75 degrees or more, It is still more preferable that it is 75-85 degrees.
If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to realize a preferable receding contact angle, it is preferable to include the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the resist film.
The thickness of the resist film is not particularly limited, but is preferably 1 to 500 nm and more preferably 1 to 100 nm because a fine pattern with higher accuracy can be formed.

(Process Y)
Step Y is a step of irradiating the film obtained in Step X with actinic rays or radiation (hereinafter, “irradiating actinic rays or radiation” is also simply referred to as “exposure”). More specifically, it is a step of selectively exposing the film so that a desired pattern is formed. Thereby, the film is exposed in a pattern, and the solubility of the film changes only in the exposed part.

Although there is no restriction | limiting in the light source wavelength used for exposure, Infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, etc. can be mentioned, Preferably it is 250 nm or less, More preferably Far ultraviolet light with a wavelength of 220 nm or less, particularly preferably 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm) , An electron beam, etc., preferably a KrF excimer laser, an ArF excimer laser, EUV or an electron beam, more preferably an ArF excimer laser.

The method for selectively exposing the film is not particularly limited, and a known method can be used. For example, a binary mask (Binary-Mask) in which the light transmittance of the light shielding portion is 0% or a halftone phase shift mask (HT-Mask) in which the light transmittance of the light shielding portion is 6% can be used.
In general, a binary mask is used in which a chromium film, a chromium oxide film, or the like is formed on a quartz glass substrate as a light shielding portion.
As the halftone phase shift mask, generally, a quartz glass substrate on which a MoSi (molybdenum silicide) film, a chromium film, a chromium oxide film, a silicon oxynitride film, or the like is formed as a light shielding portion is used.
In the present invention, the exposure is not limited to exposure through a photomask, and selective exposure (pattern exposure) may be performed by exposure without using a photomask, for example, drawing with an electron beam or the like.
This process Y may include multiple times of exposure.

In the process Y, an immersion exposure method can be applied. The immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.
When performing immersion exposure, (1) after forming a film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Before the step of heating, a step of washing the surface of the membrane with an aqueous chemical solution may be performed.

The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
When water is used, an additive (liquid) that reduces the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the film on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.

As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.
On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

The electrical resistance of the water used as the immersion liquid is preferably 18.3 MΩcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.
In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. The contact angle of the immersion liquid with respect to the actinic ray-sensitive or radiation-sensitive film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

(Process Z)
Step Z is a step of developing the film to form pattern 1. By implementing this process, the pattern 1 containing a desired organic substance is formed.
The type of developer used for development is not particularly limited. For example, an alkali developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer) can be used.
Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyl Tetraalkylammonium hydroxide such as methylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, etc. Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used. Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution. The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkali developer is usually from 10.0 to 15.0. The alkali concentration and pH of the alkali developer can be appropriately adjusted and used. The alkali developer may be used after adding a surfactant or an organic solvent.
As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

As the organic developer, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents 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, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, 2 -Methyl hydroxyisobutyrate, 3-methylbutyl acetate and the like can be mentioned.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.

Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be mentioned.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent 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, with respect to 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 ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

  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 developer to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  The organic developer may contain a basic compound. Examples of the basic compound include nitrogen-containing basic compounds, for example, nitrogen-containing compounds described in JP-A-2013-11833, particularly <0021> to <0063>. When the organic developer contains a basic compound, an improvement in contrast during development, suppression of film loss, and the like can be expected.

As the organic solvent contained in the developer, it is preferable to use an organic solvent having a reduced peroxide content. This improves the storage stability of the actinic ray-sensitive or radiation-sensitive resin composition. The peroxide content in the organic solvent is preferably 2.0 mmol% or less, more preferably 1.0 mmol% or less, still more preferably 0.5 mmol% or less, and peroxide. It is particularly preferred that the product is not substantially contained.
The organic solvent used as a rinsing liquid described later, the organic solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition, and the organic solvent contained in the spacer-forming composition are also contained in the peroxide. It is preferable to satisfy the amount range.

  As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.

When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.

In step Z, a step of developing using a developer containing an organic solvent (organic solvent developing step) and a step of developing using an aqueous alkali solution (alkali developing step) may be used in combination. Thereby, a finer pattern can be formed.
In the present invention, a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 <0077). The same mechanism as>.
In the pattern forming method of the present invention, the order of the alkali development step and the organic solvent development step is not particularly limited, but it is more preferable to perform the alkali development before the organic solvent development step.

After the alkali development step and / or the organic solvent development step, it is preferable to include a step of rinsing with a rinsing liquid (rinsing step).
The rinsing liquid used in the rinsing 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. The rinse liquid contains at least one organic solvent selected from the group consisting of hydrocarbon solvents (for example, undecane), ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. It is preferable to use a rinse solution.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.

  Among them, more preferably, performing a washing step using a rinse liquid containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, Preferably, the step of washing with a rinse solution containing an alcohol solvent or an ester solvent is performed, particularly preferably the step of washing with a rinse solution containing a monohydric alcohol is performed, most preferably carbon. A cleaning step is performed using a rinsing solution containing a monohydric alcohol of several 5 or more.

  Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 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 and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.

A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

  The vapor pressure of the rinsing solution used after the step of developing with a developer 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 at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the rinse solution.
In the rinsing step, washing is performed using the rinse liquid. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  The organic developer, alkali developer, and / or rinse solution used in the present invention preferably have few impurities such as various fine particles and metal elements. In order to obtain such chemicals with few impurities, these chemicals are manufactured in a clean room, and filtered with various filters such as Teflon (registered trademark) filters, polyolefin filters, ion exchange filters, etc. It is preferable to reduce impurities. As for the metal element, the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are all preferably 10 ppm or less, and preferably 5 ppm or less. More preferred.

  In addition, the storage container for the developer and the rinsing liquid is not particularly limited, and containers such as polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin that are used for electronic materials can be used as appropriate. In order to reduce impurities eluted from the container, it is also preferable to select a container having a small amount of components eluted from the inner wall of the container into the chemical solution. Examples of such a container include a container whose inner wall is a perfluoro resin (for example, FluoroPure PFA composite drum manufactured by Entegris (wetted inner surface; PFA resin lining), steel drum can manufactured by JFE (wetted inner surface; zinc phosphate coating)) ) And the like.

<Process B>
Step B is a step of forming a film 2 that covers the pattern 1. More specifically, as shown in FIG. 1B, the film 2 (14) is arranged so as to cover the surface of the pattern 1 (12) that is not in contact with the substrate 10. In FIG. 1B, the film 2 is arranged so as to fill the space between the patterns 1. However, the present invention is not limited to this mode. If the film 2 covers the pattern 1, the pattern 1 The film 2 may not be buried in between.
The method for 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 “spacer agent”) used for forming the film 2 into contact with the pattern 1. As a method for contacting the film-forming component, for example, a method in which a substrate provided with the pattern 1 is immersed in a tank filled with the film-forming component for a certain time (dip method), the film-forming component is raised on the surface of the pattern 1 by surface tension. A method of developing by standing still for a certain time (paddle method), a method of spraying a film-forming component on the surface of pattern 1 (spray method), and a pattern 1 on a substrate having a pattern 1 rotating at a constant speed at a constant speed. A method of continuously discharging the film forming component while scanning the discharge nozzle (dynamic dispensing method), a method of applying the film forming component on the pattern 1 to form the film 2 on the pattern 1, and a pattern 1 in the vapor of the film forming component It is possible to apply a method of exposing

When forming the film 2, it is preferable to cause an interaction between the pattern 1 and the film forming component. For example, when the actinic ray-sensitive or radiation-sensitive resin composition used for forming the pattern 1 contains a resin that decomposes by the action of an acid to generate a polar group, interaction with the polar group ( For example, chemical bonds, electrostatic interactions, hydrogen bonds, dipole interactions, coordination bonds, etc. In this specification, chemical bonds are also one of the interactions. Is preferred. 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. Since this interaction film is a film formed by contact between the pattern 1 and the film 2, it can be a finer pattern. Since the interaction film is different in solubility in the solvent from the patterns 1 and 2, only the interaction film remains on the substrate by removing the excess pattern 1 and the excess film 2 as described later. Can be made.
A film forming component that does not cause the interaction as described above can also be used.
Further, the film forming component itself may be a component that crosslinks.

  As a method for forming the film 2, the composition used for forming the film 2 (hereinafter, also referred to as “spacer-forming composition”) is easy to control the film thickness of the film 2 among the methods described above. ) On the pattern 1 to form the film 2 (hereinafter also referred to as “coating method”). Hereinafter, the aspect of the coating method will be described in detail.

The method for applying the spacer forming composition is not particularly limited, and a known method can be used. For example, spin coating is preferably used.
The type of the component contained in the composition for forming a spacer is not particularly limited as long as the component capable of forming the film 2 described above is included, but in terms of the line width uniformity of the pattern to be formed, It is preferable that a film forming component and an organic solvent are contained.
Further, the spacer forming composition may contain water, but the water content thereof is 10 mass with respect to the total mass of the spacer forming composition in terms of the line width uniformity of the pattern to be formed. % Or less is preferable and 5 mass% or less is more preferable. In addition, the said moisture content is content (mass%) with respect to the composition total mass of the water contained in a composition in other words.

Details of the film-forming component will be described later.
The kind in particular of the organic solvent contained in the composition for spacer formation is not restrict | limited, A well-known organic solvent can be used. For example, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, etc., exemplified by the organic developer used in Step Z described above, or hydrocarbon solvents Is mentioned. Examples of each solvent are as described above. Among these, at least one of an alcohol solvent and an ether solvent is preferable because the pattern shape to be formed is more excellent.
The content of the film forming component and the organic solvent in the spacer forming composition is not particularly limited, but the content of the organic solvent is preferably 700 to 8000 parts by mass, and 1500 to 3000 parts by mass with respect to 100 parts by mass of the film forming component. Part is more preferred.

In step B, it is preferable to provide a heating step of performing a heat treatment after applying the spacer forming composition as described above and before step C described later. By performing the heat treatment, the film 2 itself can be cured, and the interaction between the pattern 1 and the film 2 can be promoted.
The conditions for the heat treatment are not particularly limited, and optimum conditions are appropriately selected depending on the types of materials used for the pattern 1 and the film 2, but the heating temperature is preferably 70 to 200 ° C, and 90 to 160 ° C. The heating time is preferably 10 to 90 seconds, more preferably 30 to 60 seconds.

<Process C>
Step C is a step of removing at least a part of the pattern 1 by etching the film 2 obtained in the step B with cluster ions to remove a part of the film 2. More specifically, as shown in FIG. 1C, cluster ions indicated by arrows are irradiated onto the film 2 (14) to be etched, and a part (upper layer part) of the film 2 (14) is irradiated. As shown in FIG. 1D, at least a part of the pattern 1 (12) (the upper part of the pattern 1 in the drawing) is exposed (exposed) as shown in FIG. As described above, when the film 2 is etched by dry etching not using cluster ions, ions penetrate into the pattern 1 located inside the film 2 and the pattern 1 is denatured (cured), which will be described later. D makes it difficult to remove the pattern 1. On the other hand, when cluster ions are used, it is possible to etch the film 2 positioned above the pattern 1 while suppressing the modification of the pattern 1.
In this step, usually, the cluster ion beam is preferably irradiated from the normal direction of the surface of the substrate 10.

Etching with the cluster ions is performed by a known apparatus that can irradiate a gas cluster ion beam (GCIB) (for example, an Ar gas cluster ion beam manufactured by ULVAC-PHI (attached to an X-ray photoelectron spectrometer)), It can be carried out by using known procedures (for example, JP-A-4-354865, U.S. Pat. No. 5,814,194, JP-A-8-321489 (particularly, paragraphs 0012 and after), JP-T-2008-502150. Gazette (especially see paragraph 0030 and after).
The gas cluster ion beam refers to a mass obtained by collecting many atoms or molecules into a lump (cluster) and ionizing and accelerating it. When high-pressure gas is ejected into a vacuum, the gas is rapidly cooled by adiabatic expansion, and a gas cluster is generated. By ionizing the gas cluster and applying an electric field, the ionized gas cluster can be accelerated. The gas cluster ions irradiated to the object are shallowly added to the substrate. Moreover, a part is scattered in parallel with the substrate surface. The unevenness formed on the substrate can be preferentially removed by a part of the gas cluster ions scattered in parallel to the substrate surface, and the substrate surface can be flattened.

Examples of the source gas include Ar, CO ₂ , O ₂ , N ₂ , NO, NO ₂ , NH ₃ , SF ₆ , CF _{4, and the} like, or a gas in which He is mixed in order to facilitate cluster generation. Available.
The condition of the acceleration voltage at the time of cluster ion beam irradiation is preferably 0.1 to 50 kV, more preferably 5 to 30 kV, and still more preferably 5 to 20 kV in that the pattern shape to be obtained is more excellent.
Moreover, as a condition of ionization current, 1 to 400 nA is preferable, 5 to 200 nA is more preferable, and 10 to 50 nA is still more preferable in that the pattern shape to be obtained is more excellent.
Furthermore, as a condition of the dose, 1 × 10 ⁵ to 1 × 10 ³⁰ ions / cm ² is preferable and 1 × 10 ¹⁰ to 1 × 10 ²⁰ ions / cm ² is more preferable in that the pattern shape to be obtained is more excellent. 1 × 10 ¹⁴ to 1 × 10 ¹⁷ ions / cm ² is more preferable.

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 with the film 2 is exposed (exposed). When part of the pattern 1 is exposed, the pattern 1 can be easily removed by the process D described later.
If necessary, a part of the pattern 1 may be etched together with the film 2.

<Process D>
The step D is a step that is performed after the step C and removes at least a part of the pattern 1 while leaving the film 2. More specifically, as shown in FIG. 1E, by performing this step, the pattern 1 (12) is removed, and the pattern of the film 2 (14) is formed on the substrate 10. In addition, as shown in FIG.1 (E), the aspect from which all the patterns 1 (12) were removed is preferable, However, It is not limited to this aspect, Pattern 1 (12) is in the range which does not impair the effect of invention. Some may remain.

  A method for removing at least a part of the pattern 1 while leaving the film 2 is not particularly limited, and a known method can be adopted. For example, using the difference in solvent property between the film 2 and the pattern 1 with respect to the solvent, a removal process using a processing solution containing a solvent, an etching process using a difference in etching resistance between the film 2 and the pattern 1, etc. Can be mentioned. Among these, a method of processing using a processing solution is preferable because the procedure is simple and the pattern shape to be formed is more excellent. 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 optimal solvent is appropriately selected depending on the components of the film 2 and the pattern 1, but water, an organic solvent, or a mixture thereof is used. Especially, the process liquid containing an organic solvent is preferable at the point which the pattern shape formed is more excellent.
The type of the organic solvent is not particularly limited, but polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and the like, exemplified as the organic developer described in the above-described Step Z, and carbonized It is preferable to use a hydrogen-based solvent.
The details of these solvents are as described above.
Further, as the processing solution, an alkaline aqueous solution exemplified as the alkaline developer described in the step Z can be used.

The removal method is not particularly limited. For example, the substrate is immersed in a bath filled with the treatment liquid for a certain period of time (dip method), the treatment liquid is raised on the surface of the substrate by surface tension, and is left for a certain period of time. Method of developing (paddle method), method of spraying treatment liquid onto the substrate surface (spray method), method of continuously discharging treatment liquid while scanning the discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic) Dispensing method) can be applied.
Moreover, you may further implement the rinse process which may be implemented at the process Z mentioned above after this process D as needed.

By performing the steps A to D, a pattern formed from the film 2 (14) is formed on the substrate 10 as shown in FIG.
In addition, this manufacturing method may have processes other than the said process AD. For example, the present manufacturing method includes a step of removing excess film 2 after step B and before step C, after step C and before step D, or after step D (hereinafter, step E) may be carried out. By carrying out this step, it is possible to remove excess film-forming components that did not adhere to the pattern 1 or did not react with the pattern 1. In particular, when an interaction occurs between the pattern 1 and the film forming component described above, the film forming component in the film 2 that does not interact with the pattern 1 is removed by performing this step. As a result, a finer pattern can be formed.
FIG. 2 shows a pattern forming method in the case where the process E is performed between the process C and the process D when an interaction film is formed by causing an interaction between the pattern 1 and the film forming component. It is typical sectional drawing which shows the procedure of each process in order.
First, as shown in FIG. 2A, pattern 1 (12) is formed on the substrate 10 by performing the above-described step A. Next, the film 2 (14) that covers 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. Next, as shown in FIG. 2 (C), by performing the step C of irradiating cluster ions from the direction of the arrow, the film 2 (14) located on the pattern 1 and a part of the interaction film 16 are formed. As shown in FIG. 2D, the pattern 1 is exposed (exposed). Next, by performing this step E, as shown in FIG. 2 (E), the surplus film 2 (film 2 containing a film-forming component that does not interact with the pattern 1) is removed, The pattern 1 and the interaction film 16 remain on the substrate 10. Furthermore, by performing the step D, the pattern 1 is removed as shown in FIG. 2F, and the pattern made of the interaction film 16 remains on the substrate 10. By carrying out the above procedure, a narrower pattern can be formed. The width of the interaction film 16 can be adjusted as appropriate depending on the film forming component used.
FIG. 2E shows a mode in which all of the surplus film 2 is removed. However, the present invention is not limited to this mode, and a part of the surplus film 2 remains within a range that does not impair the effects of the present invention. It is also possible to use this mode. In other words, an aspect in which at least a part of the surplus film 2 is removed may be employed.

The method for removing the surplus film 2 is not particularly limited, but it is preferable to perform the removal using a treatment liquid capable of dissolving the film 2.
The removal method is not particularly limited. For example, a method of immersing the substrate in a tank filled with a treatment solution capable of dissolving the film 2 (dip method), a treatment solution capable of dissolving the film 2 on the substrate surface, and the like. Method of developing by padding by surface tension and standing for a certain period of time (paddle method), method of spraying treatment liquid capable of dissolving film 2 on substrate surface (spray method), constant on substrate rotating at constant speed It is possible to apply a method (dynamic dispensing method) or the like that continues to discharge a processing solution capable of dissolving the film 2 while scanning the discharge nozzle at a speed.

The type of the processing solution capable of dissolving the film 2 is not particularly limited, and an optimal solution is appropriately selected depending on the type of film constituents constituting the film 2. For example, the alkaline developer described in the above step Z is exemplified. And the organic solvents exemplified as the organic developer. Of these, water or an alcohol solvent is preferable.
The contact time between the treatment liquid capable of dissolving the membrane 2 and the membrane 2 is not particularly limited, but is preferably 5 to 180 seconds and more preferably 15 to 90 seconds from the viewpoint of achieving both productivity and removability.

  Moreover, you may further implement the rinse process which may be implemented at the process Z mentioned above after the said 1st removal process as needed.

<Description of various materials>
Below, the actinic-ray-sensitive or radiation-sensitive resin composition used at the process X mentioned above and the film formation component used at the process B are explained in full detail.

<Actinic ray-sensitive or radiation-sensitive resin composition>
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin that decomposes by the action of an acid to generate a polar group.
In one embodiment, the actinic ray-sensitive or radiation-sensitive resin composition further contains at least one of a compound that generates an acid upon irradiation with actinic rays or radiation, a hydrophobic resin, a basic compound, and a surfactant. You may do it.
Hereinafter, each of these components will be described.

[Resin that decomposes by the action of acid to produce polar groups]
A resin that decomposes by the action of an acid to generate a polar group (hereinafter also referred to as “resin (A)”) is a resin that changes its polarity by the action of an acid, and has a solubility in an organic solvent developer by the action of an acid. Is a resin whose solubility in an alkaline developer is increased.
Resin (A) is a group (hereinafter also referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate a polar group in the main chain or side chain of the resin, or both of the main chain and side chain. It is preferable to have.
The acid-decomposable group preferably has a structure protected by a group capable of decomposing and leaving a polar group by the action of an acid.

  The polar group is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent, but a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group. , Sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkyl Sulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group and other acidic groups (2.38 mass% tetra, conventionally used as a resist developer) Methylan Group dissociates in onium hydroxide aqueous solution), or alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). An aliphatic alcohol substituted with a functional group (for example, a fluorinated alcohol group (such as a hexafluoroisopropanol group)) is excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.
Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl 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 monocyclic or polycyclic. The number of carbon atoms is preferably 3-20.
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 combining 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, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

[Repeating unit having acid-decomposable group]
The resin (A) preferably has a repeating unit having an acid-decomposable group.
In one embodiment, the resin (A) contains, as a repeating unit having an acid-decomposable group, a repeating unit (AI) that is decomposed by an acid to generate a carboxyl group (hereinafter also referred to as “repeating unit (AI)”). It is preferable to have a repeating unit represented by the following general formula (aI) or (aI ′).

In the general formulas (aI) and (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 represents an alkyl group or a cycloalkyl group. Two of Rx _{1 to} Rx ₃ may combine to form a ring structure. The ring structure may contain a hetero atom such as an oxygen atom in the ring.
Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and a phenylene group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

T in the general formula (aI) is preferably a single bond or a —COO—Rt— group, more preferably a —COO—Rt— group, from the viewpoint of insolubilization of the resist with respect to the organic solvent developer. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
T in the general formula (aI ′) is preferably a single bond.

The alkyl group of _Xa1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group for _Xa1 preferably has 1 to 4 carbon atoms, and is preferably a methyl group.
X _a1 is preferably a hydrogen atom or a methyl group.
The alkyl group for Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched.
Examples of the cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ include polycyclic rings such as a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. Are preferred.
The ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ includes a monocyclic cycloalkane ring such as cyclopentyl ring and cyclohexyl ring, norbornane ring, tetracyclodecane ring, tetracyclododecane ring, adamantane ring A polycyclic cycloalkyl group such as is preferable. A monocyclic cycloalkane ring having 5 or 6 carbon atoms is particularly preferable.
Rx ₁ , Rx ₂ and Rx ₃ are preferably each independently an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a cycloalkyl group (3 to 8 carbon atoms), a halogen atom, an alkoxy group (carbon). Number 1-4), a carboxyl group, an alkoxycarbonyl group (carbon number 2-6) etc. are mentioned, and carbon number 8 or less is preferable. Among these, from the viewpoint of further improving the dissolution contrast with respect to a developer containing an organic solvent before and after acid decomposition, a substituent having no hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom is more preferable ( For example, it is more preferable that it is not an alkyl group substituted with a hydroxyl group, etc.), a group consisting of only a hydrogen atom and a carbon atom is more preferable, and a linear or branched alkyl group or a cycloalkyl group is particularly preferable. preferable.

Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited to these specific examples.
In specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb are each an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec -Butyl group, t-butyl group, etc.). Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituent that each group such as Rx _{1 to} Rx ₃ may have.

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

In one embodiment, the resin (A) preferably contains, as a repeating unit having an acid-decomposable group, a repeating unit having a total of 4 to 9 carbon atoms at the site decomposed by the acid. More preferably, in the above-described general formula (aI), the —C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) moiety has 4 to 9 carbon atoms.
More preferably, in the general formula (aI), all of Rx ₁ , Rx ₂ and Rx ₃ are methyl groups or ethyl groups, or an aspect represented by the following general formula (aII).

In general formula (aII),
R ₃₁ represents a hydrogen atom or an alkyl group.
R ₃₂ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group.
R ₃₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded. In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.
Here, the total number of carbon atoms of R ₃₂ and R ₃₃ is 8 or less.

The alkyl group for R ₃₁ may have a substituent, and examples of the substituent include a fluorine atom and a hydroxyl group.
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, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group.

The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably a 3- to 8-membered ring, and more preferably a 5- or 6-membered ring.
In the monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom, examples of the hetero atom that can form the ring include an oxygen atom and a sulfur atom. Examples of the group having a hetero atom include a carbonyl group and the like. Can be mentioned. However, the group having a hetero atom is preferably not an ester group (ester bond).
The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably formed only from the carbon atom and the hydrogen atom.
In another embodiment, the resin (A) is a repeating unit having an acid-decomposable group and a repeating unit having an acid-decomposing site containing 10 to 20 carbon atoms and a polycyclic structure. Unit (aIII) may be included.
As the repeating unit (aIII) having 10 to 20 carbon atoms in the acid decomposition site and containing a polycyclic structure in the acid decomposition site, Rx ₁ , Rx ₂ and Rx in the above general formula (aI) can be used. _In an embodiment in which one of ₃ is a group having an adamantane skeleton and the remaining two are linear or branched alkyl groups, or in general formula (aI), _{two of} Rx ₁ , Rx ₂ and Rx ₃ are bonded An embodiment in which an adamantane structure is formed and the remaining one is a linear or branched alkyl group is preferred.

  Moreover, resin (A) may have a repeating unit which decomposes | disassembles by the effect | action of an acid and produces an alcoholic hydroxyl group as represented below as a repeating unit which has an acid-decomposable group.

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

One type of repeating unit having an acid-decomposable group that can be contained in the resin (A) may be used, or two or more types may be used in combination.
When the resin (A) contains a repeating unit having two or more kinds of acid-decomposable groups, for example, in the above general formula (aI), all of Rx ₁ , Rx ₂ and Rx ₃ are methyl groups or ethyl groups The repeating unit of the embodiment or the embodiment represented by the general formula (aII) and the repeating unit having 10 to 20 carbon atoms in the acid decomposition site and containing a polycyclic structure in the acid decomposition site ( A combination with a repeating unit represented by aIII) is preferred.

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

The content of the repeating unit represented by the general formula (aI) is preferably from 30 to 80 mol%, more preferably from 40 to 75 mol%, more preferably from 45 to 70 mol, based on all the repeating units constituting the resin (A). % Is particularly preferable, and 50 to 70 mol% is most preferable.
The proportion of the repeating unit (aIII) in all repeating units having an acid-decomposable group is preferably 3 to 50 mol%, more preferably 5 to 40 mol%, and most preferably 5 to 30 mol%.

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

  Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure is preferable. Other ring structures are condensed in a form that forms a bicyclo structure or spiro structure in a member ring lactone structure, or other rings that form a bicyclo structure or a spiro structure in a 5- to 7-membered ring sultone structure Those having a condensed ring structure are more preferable. A lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3), More preferably, it has a repeating unit having A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), especially A preferred lactone structure is (LC1-4). By using such a specific lactone structure, LER and development defects are improved.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (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, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.

  The repeating unit having a lactone structure or a sultone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof 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 general formula (III).

In the general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .
When there are a plurality of Zs, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond,

Or a urea bond,

Represents. Here, each R 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, and 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 cycloalkylene group represented by 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 for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.
The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxyl group, An alkoxy group is mentioned.
R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

A preferred chain alkylene group for R ₀ is a chain alkylene having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. A preferable cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.

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. As specific examples, general formulas (LC1-1) to ( LC1-21) and a lactone structure or a sultone structure represented by any one of (SL1-1) to (SL1-3), and among these, a structure represented by (LC1-4) is particularly preferable. preferable. Further, n ₂ in (LC1-1) to (LC1-21) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent is more preferable.

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

  In order to enhance the effect of the present invention, it is possible to use two or more kinds of repeating units having a lactone structure or a sultone structure 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 5 to 60 mol% with respect to all the repeating units in the resin (A). Is more preferable, more preferably 5-55 mol%, still more preferably 10-50 mol%.

[Repeating unit having a cyclic carbonate structure]
Moreover, the resin (A) may have 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 general formula (A-1).

In general formula (A-1),
R _A ¹ represents a hydrogen atom or an alkyl group.
R _A ² each independently represents a substituent when n is 2 or more.
A represents a single bond or a divalent linking group.
Z represents an atomic group that forms a monocyclic or polycyclic structure together with a group represented by —O—C (═O) —O— in the formula.
n represents an integer of 0 or more.

General formula (A-1) is demonstrated in detail.
The alkyl group represented by R _A ¹ may have a substituent such as 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 amino group, or an alkoxycarbonylamino group. Preferably it is a C1-C5 alkyl group, and a C1-C5 linear alkyl group; C3-C5 branched alkyl group etc. can be mentioned. The alkyl group may have a substituent such as a hydroxyl group.

  n is an integer of 0 or more representing the number of substituents. For example, n is preferably 0 to 4, and more preferably 0.

  Examples of the divalent linking group represented by A include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. As an alkylene group, a C1-C10 alkylene group is preferable and a C1-C5 alkylene group is more preferable.

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

As a monocycle containing -O-C (= O) -O- represented by Z, for example, in the cyclic carbonate represented by the following general formula (a), n _A = 2 to 4 5 to 7-membered ring, and it is preferably a 5- or 6-membered ring _(n a = 2 or 3), more preferably a 5-membered ring _(n a = 2).

  Examples of the polycycle including —O—C (═O) —O— represented by Z include, for example, a cyclic carbonate represented by the following general formula (a) together with one or more other ring structures. Examples include a structure forming a condensed ring and a structure forming a spiro ring. The “other ring structure” that 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 repeating units represented by the general 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 general formula (A-1)) is based on the total repeating units constituting the resin (A). 3 to 80 mol%, preferably 3 to 60 mol%, more preferably 3 to 30 mol%, and most preferably 10 to 15 mol%. By setting it as such a content rate, the developability as a resist, low defect property, low LWR, low PEB temperature dependence, a profile, etc. can be improved.

  Although the specific example of the repeating unit represented by general formula (A-1) below is given, this invention is not limited to these.

Incidentally, _R ^{A 1} in the following specific examples are the same meaning as _R ^{A 1} in the general formula (A-1).

[Repeating unit having a hydroxyl group, a cyano group or a carbonyl group]
The resin (A) may have a repeating unit having a hydroxyl group, a cyano group, or a carbonyl group. This improves the substrate adhesion and developer compatibility.

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

Further, the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group is preferably different from the repeating unit having an acid-decomposable group (that is, a repeating unit which is stable with respect to an acid). Preferably).
The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group is preferably an adamantyl group, a diadamantyl group or a norbornane group.

  More preferably, the repeating unit represented by any of the following general formulas (AIIa) to (AIIe) can be exemplified.

In the formula, R _X 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 cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. As an alkylene group, a C1-C10 alkylene group is preferable, A C1-C5 alkylene group is more preferable, For example, a methylene group, ethylene group, a propylene group, etc. are mentioned.
In one embodiment of the present invention, 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, but at least one of the plurality of Rp represents a hydroxyl group or a hydroxyalkyl group.

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

  Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

  In addition, the monomers described in [0011] and thereafter in International Publication 2011/122336, or the corresponding repeating units can be used as appropriate.

[Repeating unit having acid group]
Resin (A) may have a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, a naphthol structure, and an aliphatic alcohol group (for example, hexafluoroisopropanol group) in which the α-position is substituted with an electron withdrawing group. It is more preferable to have a repeating unit having a carboxyl group. By containing the repeating unit having an acid group, the resolution in the contact hole application is increased. The repeating unit having an acid group includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acid group in the main chain of the resin through a linking group. Either a repeating unit that is bonded, or a polymerization initiator or chain transfer agent having an acid group, is introduced at the end of the polymer chain during polymerization, and the linking group is a monocyclic or polycyclic cyclic hydrocarbon structure. You may have. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

The resin (A) may or may not contain a repeating unit having an acid group. However, when it is contained, the content of the repeating unit having an acid group is relative to all the repeating units in the resin (A). It is preferably 25 mol% or less, and more preferably 20 mol% or less. When resin (A) contains the repeating unit which has an acid group, content of the repeating unit which has an acid group in resin (A) is 1 mol% or more normally.
Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.

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

[Repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability]
The resin (A) in the present invention can further have a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, an acid group, a hydroxyl group, or a cyano group) and does not exhibit acid decomposability. As a result, the elution of low molecular components from the resist film to the immersion liquid during immersion exposure can be reduced, and the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. . Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In general 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 an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

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

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.
These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done.

  The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. 1-50 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 5-50 mol%, More preferably, it is 5-20 mol%.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Repeating unit having an aromatic ring]
In the case where the actinic 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 beam having a wavelength of 50 nm or less (for example, EUV), resin (A) It is preferable to have a unit having an aromatic ring as represented by a hydroxystyrene repeating unit.
The repeating unit having an aromatic ring is not particularly limited, and is also exemplified in the above description of each repeating unit, but a styrene unit, a hydroxystyrene unit, a phenyl (meth) acrylate unit, a hydroxyphenyl (meth) acrylate. Examples include units. More specifically, the resin (A) is a resin having a hydroxystyrene-based repeating unit and a hydroxystyrene-based repeating unit protected by an acid-decomposable group, a repeating unit having the aromatic ring, and (meth) Examples thereof include a resin having a repeating unit in which the carboxylic acid moiety of acrylic acid is protected by an acid-decomposable group. In particular, particularly in the case of EUV exposure, since high sensitivity is generally required, the resin (A) preferably contains a repeating unit containing a protective group that easily undergoes acid decomposition. Specific examples of the repeating unit include -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ) or -C (R ₀₁ ) (R ₀₂ ) ( A compound represented by OR ₃₉ ) (a structure commonly referred to as an acetal type protecting group) is preferred.

  Moreover, the aspect with which the structure corresponding to the acid generator mentioned later was carry | supported may be sufficient as resin (A) in one form. Specifically, as such an embodiment, a structure described in JP2011-248019A (particularly, a structure described in paragraphs 0164 to 0191, a structure included in the resin described in the example in paragraph 0555). And the repeating unit (R) described in paragraphs 0023 to 0210 of JP2013-80002A, and the contents thereof are incorporated in the present specification. Even if the resin (A) has a structure corresponding to the acid generator, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is not further supported on the resin (A). An acid generator (that is, a compound (B) described later) may be included.

  Examples of the repeating unit having a structure corresponding to the acid generator include the following repeating units, but are not limited thereto.

The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is dry etching resistant, standard developer suitability, substrate adhesion, resist profile, and more sensitive in addition to the above repeating structural units. Various repeating structural units can be included for the purpose of adjusting the resolution, heat resistance, sensitivity, and the like, which are general necessary characteristics of the light-sensitive or radiation-sensitive resin composition.
Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, performance required for the resin used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Fine adjustment such as dry etching resistance can be performed.
As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

In the resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the molar ratio of each repeating structural unit is the dry etching resistance or standard development of the actinic ray-sensitive or radiation-sensitive resin composition. It is appropriately set to adjust the liquid aptitude, substrate adhesion, resist profile, and further the resolving power, heat resistance, sensitivity, etc., which are general required performances of the actinic ray-sensitive or radiation-sensitive resin composition.
Resin used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention from the viewpoint of transparency to ArF light when the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure (A) 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, ideal Is preferably 0 mol%, that is, having no aromatic group), and the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

  The form of the resin (A) in the present invention may be any of random type, block type, comb type, and star type. Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a hydrophobic resin (HR) described later, the resin (A) is from the viewpoint of compatibility with the hydrophobic resin (HR). It does not contain a fluorine atom or a silicon atom (specifically, the ratio of the repeating unit having a fluorine atom or a silicon atom in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 Mol%).
The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably one in which all repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.

  The resin (A) in the present invention can be synthesized according to a conventional method (for example, by a method commonly used in the field of polymer synthesis such as radical polymerization, living radical polymerization, anionic polymerization, and cationic polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the actinic-ray sensitive or radiation sensitive resin composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 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 is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied.
For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used for the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and depending on the type of polymer, hydrocarbon, halogenated hydrocarbon, nitro compound , Ethers, ketones, esters, carbonates, alcohols, carboxylic acids, water, mixed solvents containing these solvents, and the like. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.
The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

  In addition, after depositing and separating the resin once, it may be dissolved again in a solvent and brought into contact with a solvent in which the resin is hardly soluble or insoluble. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is contacted, the resin is precipitated (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent. Preparation (step c), and then contacting the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably not more than 5 times the volume amount). It may be a method including depositing a solid (step d) and separating the deposited resin (step e).

Further, in order to suppress the aggregation of the resin after the preparation of the actinic ray-sensitive or radiation-sensitive resin composition, for example, as described in JP-A-2009-037108, the synthesized resin is used as a solvent. You may add the process of melt | dissolving to make a solution and heating the solution at 30 degreeC-about 90 degreeC for about 30 minutes-4 hours.
By these purification steps, it is preferable to reduce as much as possible unreacted low molecular components (monomers and oligomers).

  The weight average molecular weight of the resin (A) in the present invention is preferably from 6000 to 50000, more preferably from 8000 to 30000, and most preferably from 10000 to 25000 as a polystyrene equivalent value by the GPC method. By setting this molecular weight range, it can be expected that the solubility in an organic developer becomes an appropriate numerical value.

  The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.

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

  In the present invention, the resin (A) may be used alone or in combination.

  Hereinafter, although the specific example (composition ratio of a repeating unit is a molar ratio) of resin (A) is given, this invention is not limited to these. In addition, below, the aspect in case the structure corresponding to an acid generator mentioned later is carry | supported by resin (A) is also illustrated.

  The resin exemplified below is an example of a resin that can be suitably used particularly during EUV exposure or electron beam exposure.

[Compound that generates acid upon irradiation with actinic ray or radiation]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a compound that generates an acid upon irradiation with an actinic ray or radiation (hereinafter also referred to as “compound (B)” or “acid generator”). May be.
The acid generator may be in the form of a low molecular compound or may be in a form incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
When the acid generator is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the acid generator is in a form incorporated into a part of the polymer, it may be incorporated into a part of the acid-decomposable resin described above, or may be incorporated into a resin different from the acid-decomposable resin.
In the present invention, the acid generator is preferably 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 general formula (ZI), (ZII), or (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

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

Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.
The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, you may have an alkyl group (preferably C1-C15) further as a substituent.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
Examples of the sulfonylimide anion include saccharin anion.
The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
Examples of other Z ⁻ include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony (for example, SbF ₆ ⁻ ), and the like.
Z ^- The at least α-position by an aliphatic sulfonate anion substituted with a fluorine atom, a fluorine atom or a fluorine atom is substituted with a group having a aromatic sulfonate anion of a sulfonic acid, an alkyl group substituted with a fluorine atom Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred.

In one embodiment of the present invention, the number of fluorine atoms contained in the anion as Z ⁻ is preferably 2 or 3.

  From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (having 3 carbon atoms). ~ 15 are preferred).
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.

These aryl groups, alkyl groups and cycloalkyl groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

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 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.
Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0046 and 0047 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, US Compounds exemplified as formulas (I-1) to (I-70) in Patent Publication No. 2003 / 0224288A1, and Formulas (IA-1) to (I) in U.S. Patent Publication No. 2003 / 0077540A1 IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).

  More preferable examples of the compound represented by the general formula (ZI) include compounds represented by the following general formula (ZI-3) or (ZI-4). First, the compound represented by general formula (ZI-3) is demonstrated.

In the general 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,
R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be linked to each other to form a ring,
R ₁ and R ₂ may combine with each other to form a ring,
R _X and R _y each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group, R _X and R _y may be connected to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
Z ⁻ represents a non-nucleophilic anion.
The alkyl group as R ₁ is preferably a linear or 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. Specific examples include branched alkyl groups. 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 C3-C20 cycloalkoxy group. The cycloalkoxy group for 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 for R ₁ may have a substituent.

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

R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ₂ and R ₃ may be connected to each other to form a ring. However, 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, cycloalkyl group and aryl group for R ₂ and R ₃ include those similar to the specific examples and preferred examples described above for R ₁ . When R ₂ and R ₃ are connected to each other to form a ring, the total number of carbon atoms contributing to the formation of the ring contained in R ₂ and R ₃ is preferably 4 to 7, and 4 or 5 It is particularly preferred that
R ₁ and R ₂ may be connected to each other to form a ring. When R ₁ and R ₂ are connected to each other to form a ring, R ₁ is an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent), and R ₂ has 1 to 4 carbon atoms. An alkylene group (preferably a methylene group or an ethylene group) is preferable, and examples of the preferable substituent include the same substituents that the aryl group as R ₁ may have. As another form in the case where R ₁ and R ₂ are connected to each other to form a ring, it is also preferable that R ₁ is a vinyl group and R ₂ is 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 2 to 30 alkenyl groups such as vinyl group, allyl group, and 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 group moiety of the 2-oxoalkyl group and alkoxycarbonylalkyl group represented by R _X and R _y, for example, those previously listed as R _X and R _y.
Examples of the cycloalkyl group part of the 2-oxocycloalkyl group and alkoxycarbonylcycloalkyl group represented by R _X and R _y include those enumerated above as R _X and Ry.

Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.
The compound represented by the general formula (ZI-3) is preferably a compound represented by the following general formulas (ZI-3a) and (ZI-3b).

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

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom. m, n, p, and q represent integers, preferably 0 to 3, more preferably 1 to 2, and particularly preferably 1. The alkylene group connecting S ⁺ and Y may have a substituent, and preferred examples of the substituent include an alkyl group.

R ₅ represents a monovalent organic group when Y is a nitrogen atom, and is absent when Y is an oxygen atom or a sulfur atom. R ₅ is preferably a group containing an electron withdrawing group, and particularly preferably a group represented by the following general formulas (ZI-3a-1) to (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, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R include the same specific examples and preferred examples as those described above for R ₁ in the general formula (ZI-3).

In the above (ZI-3a-1) to (ZI-3a-4), * represents a bond connected to a nitrogen atom as Y in the compound represented by the general 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, cycloalkyl group and aryl group for R ₄ include those similar to the specific examples and preferred examples described above for R ₁ .
Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.
Specific examples of the cation moiety of the compound represented by the general formula (ZI-3) are shown below.

  Next, the compound represented by general formula (ZI-4) is demonstrated.

In general formula (ZI-4),
R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have a substituent.
When there are a plurality of R _{14 s,} each independently represents a group having 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 cycloalkyl group. Represent. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring, and the atoms constituting the ring may include heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom. These groups may have a substituent.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

In General Formula (ZI-4), the alkyl groups represented by R ₁₃ , R _14, and R ₁₅ are linear or branched and preferably have 1 to 10 carbon atoms.

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

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

The alkoxycarbonyl group for 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.

The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

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

Examples of the substituent that each of the above 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, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc.
As a ring structure that two R ₁₅ may be bonded to each other, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4) is particularly preferable. Includes a 5-membered ring (that is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. This divalent R ₁₅ may have a substituent. 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, an alkoxycarbonyl group. Group, alkoxycarbonyloxy group and the like. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.

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

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

  Specific examples of the cation structure possessed by the compound represented by the general formula (ZI-3) or (ZI-4) described above include the above-mentioned JP-A-2004-233661, JP-A-2003-35948, In addition to cationic structures such as compounds exemplified in U.S. Patent Application Publication No. 2003 / 0224288A1 and U.S. Patent Application Publication No. 2003 / 0077540A1, for example, paragraphs 0046 and 0047 of JP2011-53360A Cation structures in chemical structures and the like exemplified in 0072-0077 and 0107-0110, cation structures in chemical structures and the like exemplified in paragraphs 0135 to 0137, 0151 and 0196 to 0199 of JP2011-53430, etc. Is mentioned.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Even the substituent, an aryl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI), alkyl groups include those which may have a cycloalkyl group.
Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.
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 general formula (2).

In general 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, and when there are a plurality of R ₇ and R ₈ , R ₇ and R ₈ are the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents an organic group containing a cyclic structure.
x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10.

The anion of the general formula (2) will be described in more detail.
Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group in the alkyl group substituted with a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, a fluorine atom or CF ₃ is preferable. In particular, it is preferable that both Xf are fluorine atoms.

R ₇ and R ₈ represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. As a specific example of the alkyl group substituted with at least one fluorine atom of R ₇ and R ₈ , CF ₃ is preferable.
L represents a divalent linking group, and represents —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, —N (Ri) — (wherein Ri represents a hydrogen atom or alkyl), an alkylene group (preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 10 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), or a plurality of these such divalent linking group formed by combining can be _{mentioned, -COO -, - OCO -,} - CO -, - SO 2 -, - CON (Ri) -, - SO 2 N (Ri) -, - CON (Ri ) - alkylene radical -, - N (Ri) CO- alkylene group -, - is preferably, -COO - - COO- alkylene group - or -OCO- alkylene group, - OCO -, - _SO 2 -, - CON (Ri) - or _-SO 2 N (Ri) - is that Is more preferable. When there are a plurality of L, they may be the same or different.
The alkyl group as Ri is preferably a linear or 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. Specific examples include straight chain alkyl groups and branched alkyl groups. 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 containing the cyclic structure of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having an aromatic attribute but also aromaticity). For example, a tetrahydropyran ring and a lactone ring structure are also included.
The alicyclic group may be monocyclic or polycyclic. Also preferred are nitrogen atom-containing alicyclic groups such as piperidine group, decahydroquinoline group, decahydroisoquinoline group. Among them, an alicyclic group having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, a decahydroquinoline group, and a decahydroisoquinoline group. And diffusibility in the film in the PEB (post-exposure heating) step can be suppressed, which is preferable from the viewpoint of improving exposure latitude.

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

  Examples of the heterocyclic group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, a furan ring, a thiophene ring, and a pyridine ring are preferable.

  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 1 to 12 carbon atoms), an aryl group (Preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group, cyano group and the like.

  The carbon constituting the organic group containing a cyclic structure (carbon contributing to ring formation) may be a carbonyl carbon.

x is preferably 1 to 8, more preferably 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.
In one embodiment of the present invention, the number of fluorine atoms contained in the anion represented by the general formula (2) is preferably 2 or 3. Thereby, the effect of the present invention can be further enhanced.

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

Z ⁻ is also preferably a sulfonate anion represented by the following general formula (B-1).

In the general formula (B-1),
R _b1 each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF ₃ ).
n represents an integer of 0 to 4.
n is preferably an integer of 0 to 3, and 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 ester bond (-OSO ₂ - or _-SO 3 -), or an combination thereof.
X _b1 is preferably an ester bond (—OCO— or —COO—) or a sulfonate ester bond (—OSO ₂ — or —SO ₃ —), and preferably an ester bond (—OCO— or —COO—). Is more preferable.
R _b2 represents an organic group having 6 or more carbon atoms.

The organic group having 6 or more carbon atoms for R _b2 is preferably a bulky group, and examples thereof include alkyl groups, alicyclic groups, aryl groups, and heterocyclic groups having 6 or more carbon atoms.
The alkyl group having 6 or more carbon atoms for R _b2 may be linear or branched, and is preferably a linear or branched alkyl group having 6 to 20 carbon atoms. Examples thereof include a linear or branched hexyl group, a linear or branched heptyl group, and a linear or branched octyl group. From the viewpoint of bulkiness, a branched alkyl group is preferable.

The alicyclic group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is used in a PEB (post-exposure heating) step. From the viewpoints of suppressing diffusibility in the film and improving MEEF (Mask Error Enhancement Factor).

The aryl group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.

The heterocyclic group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic, but polycyclic can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, and a dibenzothiophene ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

The substituent having 6 or more carbon atoms for R _b2 may further have a substituent. Examples of the further substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic, or spiro ring). And preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, And sulfonic acid ester groups. In addition, carbonyl carbon may be sufficient as the carbon (carbon which contributes to ring formation) which comprises the above-mentioned alicyclic group, an aryl group, or a heterocyclic group.

  Specific examples of the sulfonate anion structure represented by the general formula (B-1) are shown below, but the present invention is not limited thereto. In addition, what corresponds to the sulfonate anion represented by General formula (2) mentioned above is also contained in the following specific example.

Z ⁻ is also preferably a sulfonate anion represented by the following general formula (AI).

In general 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 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 an alkyl group having 1 to 5 carbon atoms. It is further more preferable, and it is especially preferable that it is a C1-C4 alkyl group.
The alkyl group may have a substituent (preferably a fluorine atom), and the alkyl group having a substituent is an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine atom. It is preferable that it is a C1-C5 perfluoroalkyl group.

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

The monovalent alicyclic hydrocarbon group represented by R ₁ preferably has 5 or more carbon atoms. The monovalent alicyclic hydrocarbon group preferably has 20 or less carbon atoms, more preferably 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) —.

  As the monocyclic alicyclic hydrocarbon group, those having 5 to 12 carbon atoms are preferable, and a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable.

  As the polycyclic alicyclic hydrocarbon group, those having 10 to 20 carbon atoms are preferable, and a norbornyl group, an adamantyl group, and a noradamantyl group are preferable.

The aryl group represented by R ₁ preferably has 6 or more carbon atoms. The aryl group preferably has 20 or less carbon atoms, more preferably 15 or less.

The heteroaryl group represented by R ₁ preferably has 2 or more carbon atoms. The heteroaryl group preferably has 20 or less carbon atoms, and more preferably 15 or less.

The aryl group and 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.
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, and a furanyl group.
Examples of the polycyclic heteroaryl group include a quinolyl group and an isoquinolyl group.

The monovalent alicyclic hydrocarbon group, aryl group, and heteroaryl group as R ₁ may further have a substituent. Examples of such a further substituent include a hydroxyl group, a halogen atom, Atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), nitro group, cyano group, amide group, sulfonamido group, alkyl group, alkoxy group, alkoxycarbonyl group, acyl group, acyloxy group, carboxy group .
R ₁ is particularly preferably a cyclohexyl group or an adamantyl group.

The divalent linking group represented by R ₂ is not particularly limited, but is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, alkylene. A group (preferably an alkylene group having 1 to 30 carbon atoms), a cycloalkylene group (preferably a cycloalkylene group having 3 to 30 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 30 carbon atoms), an arylene group (preferably May be a C6-C30 arylene group), a heteroarylene group (preferably a C2-C30 heteroarylene group), or a group in which two or more of these are combined. The above alkylene group, cycloalkylene group, alkenylene group, arylene group and heteroarylene group may further have a substituent, and specific examples of such a substituent include a monovalent alicyclic ring as R _1. The substituents that the hydrocarbon group, aryl group, and heteroaryl group may further have are the same as those described above.

The divalent linking group represented by R ₂ is preferably an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or a heteroarylene group, more preferably an alkylene group, and further an alkylene group having 1 to 10 carbon atoms. An alkylene group having 1 to 5 carbon atoms is preferable.

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, and still more preferably 1 to 4 carbon atoms. 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 1 to 4 carbon atoms. More specifically, Rf is preferably a fluorine atom or CF ₃ .
n ₁ is preferably 1.
n ₂ is preferably 1.
Although the preferable specific example of the sulfonate anion represented by the said general formula (AI) is given to the following, this invention is not limited to these. In addition, what corresponds to the sulfonate anion represented by General formula (2) mentioned above is also contained in the following specific example.

The non-nucleophilic anion Z ⁻ may be a disulfonylimide acid anion represented by the general formula (2 ′).

In general formula (2 ′),
Xf is as defined in the general formula (2), and preferred examples are also the same. In the general formula (2 ′), two Xf's may be linked to each other to form a ring structure.
Z ^- The disulfonylimide anion of, preferably a bis (alkylsulfonyl) imide anion.
The alkyl group in the bis (alkylsulfonyl) imide anion is preferably an alkyl group having 1 to 5 carbon atoms.
Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), and may form a ring together with the imide group and the two sulfonyl groups. The ring structure that may be formed by the bis (alkylsulfonyl) imide anion is preferably a 5- to 7-membered ring, and more preferably a 6-membered ring.

These alkyl groups and alkylene groups formed by connecting two alkyl groups to each other can have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryl Examples thereof include an oxysulfonyl group and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
Examples of the acid generator further include compounds represented by the following general formula (ZV).

In general formula (ZV),
R ₂₀₈ represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Specific examples of the aryl group of R ₂₀₈ include the same examples as the specific examples of the aryl group as R _{201 to} R ₂₀₃ in the general formula (ZI).
Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ include the same examples as the specific examples of the alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ in the general formula (ZI).

The alkylene group of A is an alkylene group having 1 to 12 carbon atoms, the alkenylene group of A is an alkenylene group having 2 to 12 carbon atoms, and the arylene group of A is an arylene group having 6 to 10 carbon atoms. , Can be mentioned respectively.
Examples of acid generators are listed below. However, the present invention is not limited to these.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator is preferably 0.1 to 30% by mass, more preferably 1 to 28% by mass, and still more preferably 3 based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. -25% by mass.

[Hydrophobic resin]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention, particularly when applied to immersion exposure, is a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (HR)” or simply “resin (HR)”). It may contain. The hydrophobic resin (HR) is preferably different from the resin (A).

As a result, the hydrophobic resin (HR) is unevenly distributed on the surface layer of the film, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to.
The hydrophobic resin may be included for various purposes even when the composition is not applied to immersion exposure. For example, when the composition is applied to EUV exposure, it is also preferable to use a hydrophobic resin in anticipation of outgas suppression and pattern shape adjustment.
The hydrophobic resin (HR) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (HR) is not necessarily required to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

Hydrophobic resin (HR) is any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in side chain portion of resin” from the viewpoint of uneven distribution in the surface layer of the film It is preferable to have the above, and it is more preferable to have two or more.
When the hydrophobic resin (HR) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin. , May be contained in the side chain.
When the hydrophobic resin (HR) contains a fluorine atom, the partial structure having a fluorine atom is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. Preferably there is.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, 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 are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms).

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.
Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

  Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH _(CF 3) OH and the like, -C _{(CF 3)} 2 OH is preferred.

  The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.

  Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.

In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents -F or -CF _3.

The hydrophobic resin (HR) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a urea bond, or a combination of two or more ( Preferably, the total carbon number is 12 or less).
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.
Hereinafter, although the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Further, as described above, the hydrophobic resin (HR) also preferably includes a CH ₃ partial structure in the side chain portion.
Here, the CH ₃ partial structure possessed by the side chain portion in the resin (HR) (hereinafter also simply referred to as “side chain CH ₃ partial structure”) includes the CH ₃ partial structure possessed by an ethyl group, a propyl group, or the like. To do.
On the other hand, a methyl group directly bonded to the main chain of the resin (HR) (for example, an α-methyl group of a repeating unit having a methacrylic acid structure) causes the surface uneven distribution of the resin (HR) due to the influence of the main chain. Since the contribution is small, it is not included in the CH ₃ partial structure in the present invention.
More specifically, the resin (HR) includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R _{11 to} R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure of the side chain moiety in the present invention.
Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R < ₁₁ > -R < ₁₄ > represents a side chain part each independently.
Examples of R _{11 to} R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of the monovalent organic group for R _{11 to} R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.
The hydrophobic resin (HR) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (V).
Hereinafter, the repeating unit represented by formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the organic group that is stable to acid is more specifically an organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). preferable.
The alkyl group of _Xb1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
X _b1 is preferably a hydrogen atom or a methyl group.

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

The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

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 monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. Preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.

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, and 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. is there.

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.

Specific examples of the hydrocarbon group having two or more CH ₃ partial structures in R ₂ include isobutyl group, t-butyl group, 2-methyl-3-butyl group, 2,3-dimethyl- 2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2 , 6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 3,5-ditert-butyl A cyclohexyl group, a 4-isopropylcyclohexyl group, a 4-tbutylcyclohexyl group, and an isobornyl group.

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

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

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

In the general formula (V), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an organic group that is stable against an acid having one or more CH ₃ partial structures, n represents an integer of 1 to 5.
The alkyl group of _Xb2 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable against acid, more specifically, it is an organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). Preferably there is.
R ₃ includes an alkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.
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.
Specific examples of the alkyl group having two or more CH ₃ partial structures in R ₃ include isopropyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl. Group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl A 3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group, and a 2,6-dimethylheptyl group;

  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 shown below. Note that the present invention is not limited to this.

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

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

  The resin (HR) is a repeating unit represented by the general formula (II), and at least one repeating unit (x) among the repeating units represented by the general formula (V) is all the repeating units of the resin (HR). By containing 90 mol% or more with respect to the unit, the surface free energy of the resin (HR) increases. As a result, the resin (HR) is less likely to be unevenly distributed on the surface of the resist film, so that the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved.

In addition, the hydrophobic resin (HR) includes the following (x) to (z) even when (i) contains a fluorine atom and / or a silicon atom, and (ii) contains a CH ₃ partial structure in the side chain portion. ) May have at least one group selected from the group of
(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) A group capable of decomposing by the action of an acid As the acid group (x), a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) ) Methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkyl) A carbonyl) methylene group, a tris (alkylsulfonyl) methylene group, and the like.

Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.
The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
The content of the repeating unit having an acid group (x) is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 5 mol% with respect to all repeating units in the hydrophobic resin (HR). 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.

As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.
Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).
The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin (HR), It is more preferably 3 to 98 mol%, and further preferably 5 to 95 mol%.

In the hydrophobic resin (HR), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group listed for the resin (A). The repeating unit having a group (z) that is decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (HR), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all repeating units in the resin (HR). Preferably it is 10-80 mol%, More preferably, it is 20-60 mol%.
The hydrophobic resin (HR) may further have a repeating unit represented by the following general formula (VI).

In general formula (VI):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with 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 an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _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 with a group containing a fluorine atom or a silicon atom.

L _c3 represents a single bond or a divalent linking group.
In general formula (VI), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
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 may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenylene group, or an ester bond (a group represented by —COO—).
The content of the repeating unit represented by the general formula (VI) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. 30 to 70 mol% is more preferable.

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

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
The content of the repeating unit represented by the general formula (CII-AB) is preferably 1 to 100 mol%, and preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is more preferably 30 to 70 mol%.

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

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

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

On the other hand, particularly when the resin (HR) includes a CH ₃ partial structure in the side chain portion, it is also preferable that the resin (HR) does not substantially contain a fluorine atom and a silicon atom. In this case, specifically, The content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, more preferably 1 mol based on all repeating units in the resin (HR). % Or less, ideally 0 mol%, that is, no fluorine atom and no silicon atom. Moreover, it is preferable that resin (HR) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom may be 95 mol% or more in all the repeating units of the resin (HR). Preferably, it is 97 mol% or more, more preferably 99 mol% or more, and ideally 100 mol%.

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

Moreover, the hydrophobic resin (HR) may be used alone or in combination.
The content of the hydrophobic resin (HR) is preferably 0.01 to 10% by mass, and 0.05 to 8% by mass with respect to the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Is more preferable, and 0.1-7 mass% is still more preferable.
The hydrophobic resin (HR), like the resin (A), naturally has few impurities such as metals, and the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably. Is more preferably 0.01 to 3% by mass and 0.05 to 1% by mass. As a result, an actinic ray-sensitive or radiation-sensitive resin composition that does not change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

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

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

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

[Basic compounds]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce changes in performance over time from exposure to heating. Although the basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(5) can be used.

(1) Basic compound (N)
Preferred examples of the basic compound include compounds (N) having a structure represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with 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.
About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
Preferable compound (N) includes guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and more preferable compound (N) includes imidazole structure, diazabicyclo structure, onium hydroxy group. Compound (N) having an alkyl group structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, etc. be able to.

  Examples of the compound (N) having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. As the compound (N) having a diazabicyclo structure, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5 , 4, 0] undec-7-ene and the like. Examples of the compound (N) having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxy. And tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. As the compound (N) having an onium carboxylate structure, the anion portion of the compound (N) having an onium hydroxide structure is converted to a carboxylate. For example, acetate, adamantane-1-carboxylate, perfluoroalkylcarboxyl Rate and the like. Examples of the compound (N) having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound (N) include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. 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 aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

Preferred examples of the basic compound (N) further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group. Examples of these compounds include compounds (C1-1) to (C3-3) exemplified in paragraph <0066> of US Patent Application Publication No. 2007 / 02245539A1.
The following compounds are also preferable as the basic compound (N).

  As the basic compound (N), in addition to the compounds described above, JP2011-22560A <0180> to <0225>, JP2012-137735A <0218> to <0219>, International Publication Pamphlet WO2011. / 158687A1 <0416> to <0438> can also be used. The basic compound (N) may be a basic compound or an ammonium salt compound whose basicity is lowered by irradiation with actinic rays or radiation.

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

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain the basic compound (N), but when it is contained, the content of the basic compound (N) is active. The amount is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the light-sensitive or radiation-sensitive resin composition.
The use ratio of the acid generator and the basic compound (N) in the actinic ray-sensitive or radiation-sensitive resin composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. . That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing resolution from being reduced due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (N) (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(2) Basic compound or ammonium salt compound (F) whose basicity is reduced by irradiation with actinic rays or radiation
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a basic compound or an ammonium salt compound (hereinafter also referred to as “compound (F)”) whose basicity is lowered by irradiation with actinic rays or radiation. It is preferable to do.
The compound (F) is preferably a compound (F-1) having a basic functional group or an ammonium group and a group that generates an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (F) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with actinic light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.
The compound (F) or (F-1) is generated by decomposing upon irradiation with actinic rays or radiation, and the compound with reduced basicity is represented by the following general formula (PA-I), (PA-II) or (PAIII) In particular, from the standpoint that excellent effects regarding LWR, local pattern dimension uniformity and DOF can be achieved at a high level, the compound represented by formula (PA-II) or (PA The compound represented by -III) is preferred.

First, the compound represented by general formula (PA-I) is demonstrated.
_{Q-A 1 - (X)} n -B-R (PA-I)
In general 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 generated 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 general formula (PA-II) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -Q 2 (PA-II)
In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ and X ₂ each independently represent —CO— or —SO ₂ —.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Next, the compound represented by general formula (PA-III) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -A 2 - (X 3) m -B-Q 3 (PA-III)
In general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, either one of Q ₁ and Q ₃ are a basic functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have 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.
B is, -N (Qx) - when, _{Q 3} and Qx may combine to form a ring.
m represents 0 or 1.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

  Hereinafter, although the specific example of a compound (F) is given, it is not limited to these. In addition to the exemplified compounds, preferred specific examples of the compound (E) include compounds (A-1) to (A-44) of US Patent Application Publication No. 2010/0233629, and US Patent Application Publication No. (A-1)-(A-23) of 2012/0156617 specification, etc. are mentioned.

It is preferable that the molecular weight of a compound (F) is 500-1000.
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain the compound (F), but when it is contained, the content of the compound (F) is actinic ray-sensitive or sensitive. 0.1-20 mass% is preferable on the basis of solid content of a radiation resin composition, More preferably, it is 0.1-10 mass%.

(3) Low molecular weight compound (G) having a nitrogen atom and a group capable of leaving by the action of an acid
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a compound having a nitrogen atom and a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (G)”). .
The group capable of leaving 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 hemiaminal ether group, It is particularly preferred.
The molecular weight of the compound (N ″) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
As the compound (G), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

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

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( Preferably it represents C1-C10) or an alkoxyalkyl group (preferably C1-C10). Rb may be connected to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are substituted with a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group, or halogen atom. It may be. The same applies to the alkoxyalkyl group represented by Rb.
Rb is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
Specific examples of the structure represented by the general formula (d-1) include a structure disclosed in paragraph <0466> of U.S. Patent Application Publication No. 2012 / 0135348A1. It is not limited.

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

In the general formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are described above as the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb may be substituted. It may be substituted with a group similar to the group.
Preferred examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) include Rb The same group as the preferable example mentioned above about is mentioned.

  Further, the heterocyclic ring formed by connecting Ra to each other preferably has 20 or less carbon atoms. For example, pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 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, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] heptane 1,5,7-triazabicyclo [4.4.0] dec-5-ene, indole, indoline, 1,2,3 -Groups derived from heterocyclic compounds such as tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds derived from linear and branched alkanes Groups derived from cycloalkanes, groups derived from aromatic compounds, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups, etc. Or a group substituted with one or more of the above.

  Specific examples of the particularly preferred compound (G) in the present invention include compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012 / 0135348A1, but are not limited thereto. Absent.

The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the low molecular compound (G) can be used singly or in combination of two or more.

  The content of the compound (G) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is 0.001 to 20% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is preferable that it is 0.001-10 mass%, More preferably, it is 0.01-5 mass%.

(4) Onium salt The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain an onium salt as a basic compound. Examples of the onium salt include onium salts represented by the following general formula (6A) or (6B). This onium salt is expected to control the diffusion of the generated acid in the resist system in relation to the acid strength of the photoacid generator usually used in the resist composition.

In general formula (6A),
Ra represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to a carboxylic acid group in the formula are excluded.
X ⁺ represents an onium cation.
In general formula (6B),
Rb represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to the sulfonic acid group in the formula are excluded.
X ⁺ represents an onium cation.

  In the organic group represented by Ra and Rb, the atom directly bonded to the carboxylic acid group or sulfonic acid group in the formula is preferably a carbon atom. However, in this case, in order to make the acid relatively weaker than the acid generated from the above-mentioned photoacid generator, the fluorine atom does not substitute for the carbon atom directly bonded to the sulfonic acid group or 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 an aralkyl group having 7 to 30 carbon atoms. Or a C3-C30 heterocyclic group etc. are mentioned. In these groups, some or all of the hydrogen atoms may be substituted.
Examples of the substituent that the alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.

Examples of the onium cation represented by X ⁺ in the general formulas (6A) and (6B) include a sulfonium cation, an ammonium cation, an iodonium cation, a phosphonium cation, and a diazonium cation. Among these, a sulfonium cation is more preferable.

  As the sulfonium cation, for example, an arylsulfonium cation having at least one aryl group is preferable, and a triarylsulfonium cation is more preferable. The aryl group may have a substituent, and the aryl group is preferably a phenyl group.

Preferred examples of the sulfonium cation and the iodonium cation include the aforementioned sulfonium cation structure of the general formula (ZI) and the iodonium structure of the general formula (ZII) in the compound (B).
A specific structure of the onium salt represented by the general formula (6A) or (6B) is shown below.

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

(5) Betaine compound Furthermore, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound included in the formula (I) of JP2012-189777A, a formula ( 1 molecule such as a compound represented by formula (I) in JP-A-2013-8020, a compound represented by formula (I) in JP-A-2012-252124, etc. A compound having both an onium salt structure and an acid anion structure (hereinafter also referred to as a betaine compound) can be preferably used. Examples of the onium salt structure include a sulfonium, iodonium, and ammonium structure, and a sulfonium or iodonium salt structure is preferable. The acid anion structure is preferably a sulfonate anion or a carboxylic acid anion. Examples of this compound include the following.

[solvent]
Examples of the solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition of the present invention include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, and alkoxypropion. Alkyl acid, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, 2-hydroxyisobutyric acid Mention may be made of organic solvents such as methyl.

Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 <0441> to <0455>.
In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.

As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether ( PGME, also known as 1-methoxy-2-propanol), ethyl lactate is more preferred. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, propylene Most preferred are carbonate and 2-heptanone.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

  The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate (PGMEA) single solvent or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate (PGMEA). Preferred specific examples of the mixed solvent include a mixed solvent containing PGMEA and a ketone solvent (cyclohexanone, 2-heptanone, etc.), a mixed solvent containing PGMEA and a lactone solvent (γ-butyrolactone, etc.), and a mixed solvent containing PGMEA and PGME. , A mixed solvent containing three types of PGMEA / ketone solvent / lactone solvent, a mixed solvent containing three types of PGMEA / PGME / lactone solvent, a mixed solvent containing three types of PGMEA / PGME / ketone solvent, etc. For example, but not limited to.

[Surfactant]
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not further contain a surfactant. When it is contained, fluorine and / or silicon surfactant (fluorine surfactant, It is more preferable to contain any one of a silicon-based surfactant and a surfactant having both a fluorine atom and a silicon atom, or two or more thereof.

When the actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a surfactant, adhesion and development defects can be obtained with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. A small resist pattern can be provided.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in <0276> of U.S. Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd.) )), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S-382 SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (Seimi Chemical Co., Ltd.), Ftop EF121, EF 22A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 230G, 218G 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.
In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

As the surfactant corresponding to the above, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), acrylate having C ₆ F ₁₃ group (or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly ( And a copolymer with oxypropylene)) acrylate (or methacrylate).

  In the present invention, surfactants other than the fluorine-based and / or silicon-based surfactants described in <0280> of US Patent Application Publication No. 2008/0248425 can also be used.

  These surfactants may be used alone or in several combinations.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is preferably relative to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). Is 0.0001 to 2 mass%, more preferably 0.0005 to 1 mass%.
On the other hand, the surface unevenness of the hydrophobic resin is increased by setting the addition amount of the surfactant to 10 ppm or less with respect to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). The surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be prepared by appropriately mixing the above components. During the preparation, a process of reducing metal impurities in the composition to the ppb level using an ion exchange membrane, a process of filtering impurities such as various particles using an appropriate filter, a deaeration process, etc. Good. Specifics of these steps are described in JP 2012-88574 A, JP 2010-189563 A, JP 2001-12529 A, JP 2001-350266 A, and JP 2002-99076 A. JP-A-5-307263, JP-A-2010-164980, WO2006 / 121162A, JP-A-2010-243866, JP-A-2010-020297, and the like.
The actinic 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 in the total weight of the composition.

<Film forming component (spacer agent)>
Below, the film formation component used at the process B is explained in full detail.

(Film forming component)
The film forming component is a material used for constituting the film 2 described above, and the type of the film forming component is not particularly limited, but it is usually preferable to use an organic substance.
As the organic substance, both a low molecular compound and a high molecular compound can be used, and a high molecular compound (a compound having a repeating unit) is more preferable. A low molecular compound is a compound having a molecular weight of less than 1000, and a high molecular compound is a compound having a molecular weight of 1000 or more.
The molecular weight of the organic substance is not particularly limited, but is preferably 1000 or more, and more preferably 10,000 or more.
The dispersity (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, because the pattern shape to be formed is more excellent.
Although Mw (weight average molecular weight) of the polymer compound is not particularly limited, 1000 to 60000 is preferable and 3000 to 25000 is more preferable in that the pattern shape to be formed is more excellent.
Further, as the film forming component, either a component capable of forming an interaction with the pattern 1 or a component other than that can be used. Moreover, the film forming component itself has crosslinkability, and the film forming components may react with each other to form the film 2 having a crosslinked structure.
Especially, it is preferable that it is a component (compound) which can form interaction with the pattern 1 as a film formation component at the point which can form an interaction film as shown in FIG. 2 mentioned above. In particular, when the actinic ray-sensitive or radiation-sensitive resin composition used for forming the pattern 1 contains a resin that decomposes by the action of an acid to generate a polar group, interaction with the polar group ( For example, it is preferable to use a film-forming component that generates a chemical bond, an electrostatic interaction, a hydrogen bond, a dipole interaction, a coordination bond, etc.).
Examples of the film forming component capable of forming an interaction as described above include at least one selected from the group consisting of an onium salt compound, a nitrogen-containing compound, and a phosphorus compound.
These compounds may be in the form of a low molecular compound or a polymer compound, but are preferably in the form of a polymer compound.

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

[Low molecular compound]
(Onium salt compound)
As the onium salt compound, a compound having an onium salt structure is intended. The onium salt structure refers to a salt structure generated by a coordinate bond between an organic component and a Lewis base. The onium salt compound mainly forms an interaction with the polar group by an ionic bond. For example, when the polar group is a carboxyl group, a cation in the onium salt compound forms an electrostatic interaction (forms an ionic bond) with the carboxyl-derived carboxyl anion (COO ⁻ ).
The type of onium salt structure is not particularly limited, and examples thereof include structures such as ammonium salts, phosphonium salts, oxonium salts, sulfonium salts, selenonium salts, carbonium salts, diazonium salts, iodonium salts having a cation structure shown below. .
In addition, the cation in the onium salt structure includes those having a positive charge on the hetero atom of the heteroaromatic ring. Examples of such onium salts include pyridinium salts and imidazolium salts.
In the present specification, the above pyridinium salt and imidazolium salt are also included as one embodiment of the ammonium salt.

The onium salt compound may be a polyvalent onium salt compound having two or more onium ion atoms in one molecule from the viewpoint that the effect of the present invention is more excellent. As the polyvalent onium salt compound, a compound in which two or more cations are linked by a covalent bond is preferable.
Examples of the polyvalent onium salt compound include diazonium salts, iodonium salts, sulfonium salts, ammonium salts, and phosphonium salts. Of these, diazonium salts, iodonium salts, sulfonium salts, and ammonium salts are preferable in view of more excellent effects of the present invention, and ammonium salts are more preferable from the viewpoint of stability.

The anion (anion) contained in the onium salt compound (onium salt structure) may be any anion as long as it is an anion, but it may be a monovalent ion or a polyvalent 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. Examples of the divalent anion include oxalate ion, phthalate ion, maleate ion, fumarate ion, tartaric acid ion, malate ion, lactate ion, sulfate ion, diglycolate ion, and 2,5-flange. Examples thereof include carboxylate ions.
More specifically, monovalent anions include Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ and 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 ( _{C 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, preferred are sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{— and the} like, more preferably containing a carbon atom. Is an organic anion.

  Below, the specific example of the cation contained in an onium salt structure is illustrated.

  Below, the specific example of the anion contained in an onium salt structure is illustrated.

  Specific examples of the onium salt structure are illustrated below.

A preferred embodiment of the onium salt compound is composed of the onium salt compound represented by the formula (1-1) and the onium salt compound represented by the formula (1-2) in that the effect of the present invention is more excellent. There may be mentioned at least one selected from the group.
In addition, the onium salt compound represented by Formula (1-1) may use only 1 type, or may use 2 or more types together. Moreover, the onium salt compound represented by Formula (1-2) may use only 1 type, or may use 2 or more types together. Moreover, you may use together the onium salt compound represented by Formula (1-1), and the onium salt compound represented by Formula (1-2).

In formula (1-1), M represents a nitrogen atom, a phosphorus atom, a sulfur atom, or an iodine atom. Especially, a nitrogen atom is preferable at the point which the effect of this invention is more excellent.
R each independently represents a hydrogen atom, an aliphatic hydrocarbon group that may contain a hetero atom, an aromatic hydrocarbon group that may contain a hetero atom, or a group in which two or more of these are combined. .
The aliphatic hydrocarbon group may be linear, branched or cyclic. In addition, the number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but 1 to 15 is preferable and 1 to 5 is more preferable in that the effect of the present invention is more excellent.
Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkene group, an alkyne group, or a group obtained by combining two or more of these.
The aliphatic hydrocarbon group may contain a hetero atom. That is, it may be a heteroatom-containing hydrocarbon group. The type of hetero atom 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 tellurium 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) -, it includes in the manner of a halogen atom, or a group composed of a combination of two or more of these.
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 tellurium atom. Of these, an oxygen atom and a sulfur atom are preferred because they are easier to handle.
Said R _<a> , R _<b> , R _<c> is each independently selected from a hydrogen atom or a C1-C20 hydrocarbon group.
t represents an integer of 1 to 3.

The number of carbon atoms contained in the aromatic hydrocarbon group is not particularly limited, but 6 to 20 is preferable and 6 to 10 is more preferable in that the effect of the present invention is more excellent.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aromatic hydrocarbon group may contain a hetero atom. The aspect in which a hetero atom is contained is as described above. In addition, when a hetero atom is contained in an aromatic hydrocarbon group, you may comprise an aromatic heterocyclic group.

  As a preferred embodiment of R, an alkyl group which may contain a heteroatom, an alkene group which may contain a heteroatom, or a cycloalkyl group which may contain a heteroatom from the viewpoint that the effects of the present invention are more excellent. And an aryl group which may contain a hetero atom.

  A plurality of R may be bonded to each other to form a ring. Although the kind of ring formed is not specifically limited, For example, a 5-6 membered ring structure can be mentioned.

Moreover, the ring formed may have aromaticity, for example, the cation of the onium salt compound represented by Formula (1-1) is a pyridinium ring represented by Formula (10) below. There may be. Furthermore, a hetero atom may be contained in a part of the ring formed. For example, a cation of the onium salt compound represented by the formula (1-1) is represented by the following formula (11). It may be an imidazolium ring.
In addition, the definition of R in Formula (10) and Formula (11) is as above-mentioned.
In formula (10) and formula (11), Rv each independently represents a hydrogen atom or an alkyl group. A plurality of Rv may be bonded to each other to form a ring.

X ⁻ represents a monovalent anion. The definition of monovalent anion is as described above.

  In formula (1-1), n represents an integer of 2 to 4. In addition, 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.

The definitions of M, R and X ⁻ in formula (1-2) are as described above. In the formula (1-2), X ^- is included two.
L represents a divalent linking group. As the divalent linking group, a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), substituted or unsubstituted divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms such as a phenylene group.), - O -, - S -, - SO 2 -, - N (R) - (R: alkyl group), -CO-, -NH-, -COO-, -CONH-, or a group in which two or more of these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.), and the like.
Among these, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group is preferable in that the effect of the present invention is more excellent.

  In formula (1-2), m represents the integer of 1-3 each independently. In addition, 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)
A nitrogen-containing compound intends a compound containing a nitrogen atom. In the present specification, the nitrogen-containing compound does not include the onium salt compound. The nitrogen-containing compound mainly forms an interaction between a 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.
As said nitrogen-containing compound, the compound represented by following General formula (6) is mentioned, for example.

In the general formula (6), R ⁴ and R ⁵ are each independently a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, a chain hydrocarbon group having 1 to 30 carbon atoms, or a carbon number of 3 It is a group formed by combining 2 or more types of -30 alicyclic hydrocarbon groups, C6-C14 aromatic hydrocarbon groups, or these groups. R ⁶ is a hydrogen atom, a hydroxyl group, a formyl 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 formed by combining two or more of these groups. n is an integer of 1 or more. However, when n is 2 or more, the 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 to form a ring structure together with the nitrogen atom to which each is bonded.

Examples of the C1-C30 chain hydrocarbon group represented by R ⁴ and R ⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by 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 R ⁴ and R ⁶ include a phenyl group, a tolyl group, and a naphthyl group.
Examples of the group formed by combining two or more of these groups represented by R ⁴ and R ⁵ include aralkyl groups having 6 to 12 carbon atoms such as benzyl, phenethyl, naphthylmethyl, and naphthylethyl groups. Can be mentioned.

Examples of the n-valent chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁶ include groups exemplified as the chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁴ and R ^5. And a group obtained by removing (n-1) hydrogen atoms from the same group.
Examples of the n-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁶ include the groups exemplified as the cyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁴ and R ⁵ above. Examples include a group obtained by removing (n-1) hydrogen atoms from the same group.
The n-valent aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ^6, for example exemplified as the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁴ and R ⁵ groups And a group obtained by removing (n-1) hydrogen atoms from the same group.
The group formed by combining two or more of these groups represented by R ⁶ is the same as the group exemplified as a group formed by combining two or more of these groups represented by R ⁴ and R ⁵ , for example. And a group obtained by removing (n-1) hydrogen atoms from the group.

The group represented by R ^{4 to} R ⁶ may be substituted. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a hydroxyl group, a carboxy group, a halogen atom, and an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Moreover, as an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.

Examples of the compound represented by the above formula (6) include (cyclo) alkylamine compounds, nitrogen-containing heterocyclic compounds, amide group-containing compounds, urea compounds and the like.
Examples of (cyclo) alkylamine compounds include compounds having one nitrogen atom, compounds having two nitrogen atoms, compounds having three or more nitrogen atoms, and the like.
Examples of (cyclo) alkylamine compounds having one nitrogen atom include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, 1-aminodecane, cyclohexylamine and the like. ;
Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, 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- tri (cyclo) alkylamines such as n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, 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-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- ( And aromatic amines such as 4-aminophenyl) -2- (4-hydroxyphenyl) propane.

  Examples of the (cyclo) alkylamine compound having two nitrogen atoms include ethylenediamine, tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and 4,4 ′. -Diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (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-quinoxalinium linoleic, 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-dimethylaminoethylacrylamide.

  Examples of the nitrogen-containing heterocyclic compound include nitrogen-containing aromatic heterocyclic compounds and nitrogen-containing aliphatic heterocyclic compounds.

  Examples of the nitrogen-containing aromatic heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- Imidazoles such as 2-methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4- Pyridines such as phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ′: 6 ′, 2 ″ -terpyridine and the like can be mentioned.

  Examples of the nitrogen-containing aliphatic heterocyclic compound include piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, proline, piperidine, piperidine ethanol, 3-piperidino -1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine 1,4-diazabicyclo [2.2.2] octane and the like.

Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt- Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-( -)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxypiperidine Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl Perazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′- Diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N ′, N′-tetra-t-butoxycarbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl- 1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl-1,9-diaminononane, N, N′-di -T-butoxycarbonyl-1,10-diaminodecane, N, N'-di-t-butoxycarbonyl-1,12-diaminododecane, N, N'-di-t- Nt such as toxoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, etc. A butoxycarbonyl group-containing amino compound;
Formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, isocyanuric Examples include acid tris (2-hydroxyethyl).

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea. Etc.

  Of these, (cyclo) alkylamine compounds and nitrogen-containing aliphatic heterocyclic compounds are preferable, and 1-aminodecane, di-n-octylamine, tri-n-octylamine, tetramethylethylenediamine, N, N-dibutylaniline, Proline is more preferred.

As a preferred embodiment of the nitrogen-containing compound, a nitrogen-containing compound containing a plurality (two or more) of nitrogen atoms (multivalent nitrogen-containing compound) is preferable. In particular, an embodiment including three or more is preferable, and an embodiment including four or more is more preferable.
Moreover, as another suitable aspect of a nitrogen-containing compound, the compound represented by Formula (3) is mentioned at the point which the effect of this invention is more excellent.

In 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), a group represented by the following formula (1B),

—NH—, —NR _W —, —O—, —S—, carbonyl group, alkylene group, alkenylene group, alkynylene group, cycloalkylene group, aromatic group, heterocyclic group, and combinations of two or more thereof A preferred example is an n-valent organic group consisting of a group. Here, in the above formulas, R _W represents an organic group, preferably an alkyl group, an alkylcarbonyl group, an alkylsulfonyl group. Further, in the above combination, heteroatoms are not linked to each other.
Of these, an aliphatic hydrocarbon group (an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group), a group represented by the above formula (1B), —NH—, and —NR _W — are preferable.

Here, the alkylene group, alkenylene group, and alkynylene group preferably have 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 2 to 12 carbon atoms. The alkylene group may be linear or branched, and may have a substituent. Here, the cycloalkylene group preferably has 3 to 40 carbon atoms, more preferably 3 to 20 carbon atoms, and still more preferably 5 to 12 carbon atoms. The cycloalkylene group may be monocyclic or polycyclic and may have a substituent on the ring.
The aromatic group may be monocyclic or polycyclic, and includes non-benzene aromatic groups. Monocyclic aromatic groups include benzene, pyrrole, furan, thiophene, and indole residues. Polycyclic aromatic groups include naphthalene, anthracene, tetracene, and benzofuran. Examples include benzothiophene residues and the like. The aromatic group may have a substituent.

  The n-valent organic group may have a substituent, and the kind thereof is not particularly limited, but an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an alkenyl group, an alkenyloxy group Alkenylcarbonyl group, alkenylcarbonyloxy group, alkenyloxycarbonyl group, alkynyl group, alkynyleneoxy group, alkynylenecarbonyl group, alkynylenecarbonyloxy group, alkynyleneoxycarbonyl group, aralkyl group, aralkyloxy group, aralkylcarbonyl group Aralkylcarbonyloxy group, aralkyloxycarbonyl group, hydroxyl group, amide group, carboxyl group, cyano group, fluorine atom and the like can be mentioned as examples.

B represents a single bond, an alkylene group, a cycloalkylene group, or an aromatic group, and the alkylene group, the cycloalkylene group, and the aromatic group may have a substituent. Here, the explanation of the alkylene group, cycloalkylene group, and aromatic group is the same as described above.
However, A and B are not both single bonds.

R _z independently represents a hydrogen atom, an aliphatic hydrocarbon group that may contain a hetero atom, or an aromatic hydrocarbon group that 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 1 to 20 is preferable and 1 to 10 is more preferable in that the effect of the present invention is more excellent.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aliphatic hydrocarbon group and the aromatic hydrocarbon group may contain a hetero atom. The definition and preferred embodiment of the heteroatom are the same as the definition of the heteroatom described in the above formula (1-1).
In addition, aliphatic hydrocarbon groups and aromatic hydrocarbon groups include substituents (eg, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, halogen atoms, Atoms) may be included.
n preferably represents an integer of 2 to 8, more preferably an integer of 3 to 8.
In addition, it is preferable that the compound represented by the said Formula (3) has three or more nitrogen atoms. In this embodiment, when n is 2, A contains at least one nitrogen atom. That A contains a nitrogen atom includes, for example, at least one selected from the group consisting of the group represented by the above formula (1B), —NH—, and —NR _W —.

  Below, the compound represented by Formula (3) is illustrated.

(Phosphorus compounds)
A phosphorus compound is a compound containing -P <(phosphorus atom). The phosphorus compound does not include an onium salt compound. The phosphorus compound mainly forms an interaction between a phosphorus atom in the compound and the polar group. For example, when the polar group is a carboxyl group, it interacts with the phosphorus atom in the phosphorus compound to form a salt.
The phosphorus compound only needs to include at least one phosphorus atom, and may include a plurality (two or more).
The molecular weight of the phosphorus compound is not particularly limited, but is preferably 70 to 500, more preferably 70 to 300, from the viewpoint that the effect of the present invention is more excellent.

  A preferred embodiment of the phosphorus compound is selected from the group consisting of a compound represented by the following formula (4-1) and a compound represented by the formula (4-2) in that the effect of the present invention is more excellent. The phosphorus compound is preferable.

Equation (4-1) and formula (4-2), R _W are each independently an aliphatic contain a hetero atom hydrocarbon group, an aromatic may contain a hetero atom hydrocarbon group Or represents a group selected from the group consisting of groups obtained by combining two or more of these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. In addition, the number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but 1 to 15 is preferable and 1 to 5 is more preferable in that the effect of the present invention is more excellent.
Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkene group, an alkyne group, or a group obtained by combining two or more of these.
The number of carbon atoms contained in the aromatic hydrocarbon group is not particularly limited, but 6 to 20 is preferable and 6 to 10 is more preferable in that the effect of the present invention is more excellent.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aliphatic hydrocarbon group and the aromatic hydrocarbon group may contain a hetero atom. The definition and preferred embodiment of the heteroatom are the same as the definition of the heteroatom described in the above formula (1-1). In addition, it is preferable that an oxygen atom is contained as a hetero atom, and it is preferable that it is contained in the aspect of -O-.

L _W represents a divalent linking group. As the divalent linking group, a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), substituted or unsubstituted divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, for example, an arylene group.), - O -, - S -, - SO 2 -, - N (R) - (R: alkyl group), -CO-, -NH-, -COO-, -CONH-, or a group in which two or more of these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.), and the like.
Among these, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group is preferable in that the effect of the present invention is more excellent.

  Below, the specific example of a phosphorus compound is illustrated.

As described above, the compound (A) may be in the form of a low molecular compound or a polymer compound, but from the viewpoint of performing multipoint interaction with a polar group, the compound (A) is in the form of a polymer compound. Preferably there is.
Hereinafter, among the onium salt compounds, nitrogen-containing compounds, and phosphorus compounds, the form of the polymer compound will be described in detail.

(Onium salt compound)
Among the onium salt compounds, the polymer compound includes a polymer having an onium salt. The polymer having an onium salt intends a polymer having an onium salt structure in a side chain or main chain. In particular, a polymer having a repeating unit having an onium salt structure is preferable.
The definition of the onium salt structure is as described above, and the definitions of the cation and the anion are also synonymous.

  A preferred embodiment of the polymer having an onium salt includes a polymer having a repeating unit represented by the formula (5-1) in that the effect of the present invention is more excellent.

In 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 1 to 20 is preferable and 1 to 10 is more preferable in that the effect of the present invention is more excellent.
L _p represents a divalent linking group. 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).
Among these, L _p is an alkylene group, an arylene group, —COO—, or a group in which two or more of these are combined (—arylene group—alkylene group—, —COO—) because the effect of the present invention is more excellent. Alkylene group- etc.) is preferable, and an alkylene group is more preferable.

A _p represents a group having an onium salt structure, specifically, by removing one hydrogen atom from an onium salt represented by any one of formulas (1-1) and (1-2) remaining It is preferable to represent a group. The residue refers to a group having a structure in which one hydrogen atom is extracted from any position in the structural formula showing an onium salt and can be bonded to L _p . Usually, one of the hydrogen atoms in R is withdrawn and becomes a group having a structure capable of binding to the above L _p .
The definition of each group in Formula (1-1) and Formula (1-2) is as above-mentioned.

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

  Although the weight average molecular weight of the said polymer is not restrict | limited in particular, 1000-30000 are preferable and 1000-10000 are more preferable at the point which the effect of this invention is more excellent.

  The weight average molecular weight and dispersity (weight average molecular weight / number average molecular weight) of the polymer are defined as polystyrene converted values by GPC measurement. In the present specification, the weight average molecular weight and the degree of dispersion are, for example, HLC-8120 (manufactured by Tosoh Corporation) and TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) as a column. ) Can be determined by using THF (tetrahydrofuran) as the eluent.

  As a suitable aspect of the repeating unit represented by Formula (5-1), the repeating unit represented by Formula (5-2) is mentioned.

In formula (5-2), the definitions of R, R _p , L _p , and X ⁻ are as described above.

  Furthermore, as a suitable aspect of the repeating unit represented by Formula (5-2), the repeating unit represented by Formula (5-3)-Formula (5-5) is mentioned.

In formula (5-3), the definitions of R, R _p , and X ⁻ are as described above.
In formula (5-4), the definitions of R, R _p , and X ⁻ are as described above.
A represents -O-, -NH-, or -NR-. The definition of R is the same as the definition of R in the above formula (1-1).
B represents an alkylene group.
In formula (5-5), the definitions of R, R _p , and X ⁻ are as described above.

(Nitrogen-containing compounds)
Among the nitrogen-containing compounds, the polymer compound is preferably a polymer having an amino group in that the effect of the present invention is more excellent. In the present specification, the “amino group” is a concept including a primary amino group, a secondary amino group, and a tertiary amino group. The secondary amino group also includes cyclic secondary amino groups such as pyrrolidino group, piperidino group, piperazino group, hexahydrotriazino group and the like.
The amino group may be contained in either the main chain or the side chain of the polymer.
Specific examples of the side chain when the amino group is contained in a part of the side chain are shown below. In addition, * represents the connection part with a polymer and / or an oligomer residue.

  Examples of the polymer having an amino group include polyallylamine, polyethyleneimine, polyvinylpyridine, polyvinylimidazole, polypyrimidine, polytriazole, polyquinoline, polyindole, polypurine, polyvinylpyrrolidone, and polybenzimidazole.

  As a suitable aspect of the polymer which has an amino group, the polymer which has a repeating unit represented by Formula (2) is mentioned.

In 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 1 to 4 is preferable and 1 to 2 is more preferable in that the effect of the present invention is more excellent.
R ² and R ³ are each independently a hydrogen atom, an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, or an aromatic group that may contain a hetero atom. Represents.
The number of carbon atoms contained in the alkyl group and cycloalkyl group is not particularly limited, but is preferably 1-20, and more preferably 1-10.
Examples of the aromatic group include aromatic hydrocarbons and aromatic heterocyclic groups.
The alkyl group, cycloalkyl group and aromatic group may contain a hetero atom. The definition and preferred embodiment of the heteroatom are the same as the definition of the heteroatom described in the above formula (1-1).
In addition, the alkyl group, cycloalkyl group, and aromatic group include substituents (eg, hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group functional group, alkoxy group, halogen Atoms) may be included.

L _a represents a divalent linking group. Definition of the divalent linking group represented by L _a is the same definition of L represented by the aforementioned formula (1-2).
Among them, as La, in which the effect of the present invention is more excellent, as L _a , an alkylene group, an arylene group, —COO—, and a group in which two or more of these are combined (-arylene group-alkylene group—, —COO— Alkylene group- etc.) is preferable, and an alkylene group is more preferable.

Incidentally, the group represented by the above R ¹ to R ^3, and, in the divalent linking group represented by L _a, substituent group (e.g., hydroxyl, etc.) may be further substituted.

  Below, the repeating unit represented by Formula (2) is illustrated.

The content of the repeating unit represented by the above formula (2) in the polymer is not particularly limited, but is preferably 40 to 100 mol% with respect to all the repeating units in the polymer in that the effect of the present invention is more excellent. 70 to 100 mol% is more preferable.
In addition, other repeating units other than the repeating unit represented by Formula (2) may be contained in the polymer.

  Although the weight average molecular weight of the polymer which has an amino group is not restrict | limited in particular, 1000-30000 are preferable and 1000-10000 are more preferable at the point which the effect of this invention is more excellent.

The film forming component may be a component other than the film forming component capable of forming the above-described interaction.
For example, a known resin can be used, and examples thereof include a resin having a repeating unit exemplified in the resin (A). The resin may contain a plurality of repeating units exemplified in the above (A).
The resin may or may not contain a repeating unit having an acid-decomposable group.
Moreover, as one of the suitable aspects of resin, resin which has a reactive group which can react with the crosslinkable group contained in the crosslinking component mentioned later is preferable. The type of the reactive group is not particularly limited, and an optimal group is appropriately selected depending on the type of the crosslinkable group. Among them, it is preferable to have an —OH group. Examples of the —OH group include a phenolic hydroxyl group (—OH group substituted with an aromatic group) and an alcoholic hydroxyl group (non-phenolic hydroxyl group). Thereby, the crosslinkability improvement with the crosslinking component mentioned later is anticipated.

As the film forming component, for example, a crosslinking component having a crosslinkable group can be preferably used. By using the crosslinking component, the mechanical strength of the film 2 formed is improved. In particular, an embodiment in which the above-described resin and a crosslinking component are used in combination is preferable.
The kind in particular of a crosslinking component is not restrict | limited, A well-known crosslinking component can be used. The type of the crosslinkable group contained in the crosslinking component is not particularly limited. For example, a hydroxyl group-containing functional group (for example, a methylol group, a dimethylolaminomethyl group, a diethylolaminomethyl group, etc.), a nitrogen atom-containing functional group (for example, Imino group, oxazoline group, imidazolium group, dimethylaminomethyl group, diethylaminomethyl group, etc.), ether group-containing functional group (for example, methoxymethyl group, ethoxymethyl group, benzyloxymethyl group, acetoxymethyl group, benzoyloxymethyl) Group, chain ether group such as morpholinomethyl group, or cyclic ether group such as oxetanyl group, glycidyl ether group and glycidyl ester group), polymerizable carbon-carbon double bond-containing functional group (for example, (meth) acryloyl group) , Vinyl group) and the like.
The cross-linking component preferably contains two or more cross-linkable groups, and more preferably contains 2 to 10 cross-linkable groups.

Preferred examples of the crosslinking component include a compound containing two or more cyclic ether groups, a compound containing two or more (meth) acryloyl groups, or a compound containing a group represented by the following formula (3). It is done.
As a crosslinking component, only 1 type may be used and 2 or more types may be used together.

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

In Formula (4), R ⁶ and R ⁷ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, or 2 to 10 carbon atoms in which R ⁶ and R ⁷ are linked to each other. R ⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

  In addition, as a compound containing 2 or more (meth) acryloyl groups, the compound represented by the following formula | equation (1) is mentioned suitably.

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

Further, as a film forming component, a base can also be used from the viewpoint of controlling the crosslinking reaction. The kind in particular of base is not restrict | limited, The said basic compound which may be contained in actinic-light sensitive or radiation sensitive resin composition is illustrated.
Further, a surfactant can also be used as the film forming component. The kind in particular of surfactant is not restrict | limited, The said surfactant which may be contained in actinic-light sensitive or radiation sensitive resin composition is illustrated.
As described above, one preferred embodiment of the film-forming component preferably includes a resin, more preferably includes a resin and a crosslinking component, and includes the resin, the crosslinking component, a base and / or a surfactant. The aspect containing is further more preferable.

The present invention also relates to an electronic device manufacturing method including the pattern forming method of the present invention described above, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).
Moreover, the pattern formation method of this invention can be used suitably also for the guide pattern formation in DSA (Directed Self-Assembly) (for example, refer to ACS Nano Vol.4 No.8 Pages4815-4823).

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

(Synthesis Example 1)
Under a nitrogen stream, 40 g of a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether was placed in a three-necked flask and heated to 80 ° C. (solvent 1). Monomers corresponding to the following repeating units were dissolved in a mixed solvent of 6/4 (mass ratio) of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether at a molar ratio of 30/10/60, respectively, A monomer solution (400 g) was prepared. Furthermore, 8 mol% of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the monomer, and the dissolved solution was added dropwise to the solvent 1 over 6 hours. After completion of dropping, the reaction was further continued at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into 3600 ml of hexane / 400 ml of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 74 g of Resin (P-1). The obtained resin (P-1) had a weight average molecular weight of 12,000 and a dispersity (Mw / Mn) of 1.6.
Resins (P-2) to (P-9) and hydrophobicity were prepared in the same manner as in Synthesis Example 1 except that the monomers corresponding to each repeating unit were used so as to have a desired composition ratio (molar ratio). Resins (N-1) to (N-3) were synthesized.

(Actinic ray sensitive or radiation sensitive resin composition (resist composition))
The components shown in Table 1 below are dissolved in the solvent shown in the same table, the total solid concentration is 3.5% by mass, and each is filtered through a polyethylene filter having a pore size of 0.05 μm, and resist compositions Ar-1 to Ar-14 was prepared.

〔resin〕
The composition ratio (molar ratio), weight average molecular weight, and dispersity of the resins used in Table 1 are shown below.

[Acid generator]
The structural formula of the acid generator is shown below.

[Basic compounds]
The structural formula of the basic compound is shown below.

[Hydrophobic resin]
The composition ratio (molar ratio), weight average molecular weight and degree of dispersion of the hydrophobic resin used in the examples are shown below.

  Abbreviations in Table 1 are as follows.

[Surfactant]
W-1: Megafuck F176 (manufactured by DIC Corporation) (fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)
W-4: PolyFox PF-6320 (made by OMNOVA) (fluorine-based)

〔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: Propylene carbonate

<Examples and Comparative Examples>
<Pattern formation: Dry exposure>
ARC29A (Nissan Chemical Co., Ltd.) for forming an organic antireflection film is applied on a silicon wafer (hereinafter also referred to as “wafer”), and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 86 nm. Formed. The resist composition (any one of Ar-1 to Ar-14) was applied thereon and baked at 100 ° C. for 60 seconds to form a resist film (film 1) having a thickness of 75 nm.
Next, an ArF excimer laser scanner (manufactured by ASML; PAS5500, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65) is passed through this resist film through a 1: 1 line and space mask with a line width of 72 nm. ) Was used.
Thereafter, the exposed resist film was heated on a hot plate at 95 ° C. for 60 seconds, and then cooled to room temperature. Next, paddle development was carried out for 20 seconds using the first developer described in Table 3 below. For examples in which the first rinse liquid was described in Table 3, the first developer described in Table 3 below was used. A pattern 1 was formed by paddle rinsing with a rinse solution for 30 seconds.

  About the example in which the composition for spacer formation described in Table 3 is applied on each pattern 1 obtained as described above, and the temperature (° C.) and time (seconds) are described in the baking column in Table 3 Baked at that temperature and time to form a film 2 having a film thickness of 200 nm (film thickness with the surface of the antireflection film as the reference plane).

Next, the obtained film 2 was etched using the following apparatus and conditions until the pattern 1 was exposed.
GCIB: An Ar gas cluster ion beam (supplied with an X-ray photoelectron spectrometer) is used.
Conditions: Acceleration voltage 5 kV, ionization current 20 nA, irradiation area 5.0 mm × 5.0 mm, use of Zalar rotation For conditions 1 to 4 in Comparative Examples 1 to 5, the following apparatus and Table 2 are used. The film 2 was etched under the conditions. Note that the etching treatment under conditions 1 to 4 is not an embodiment using cluster ions.
As the etching apparatus, Etch Centura DPS having a high frequency plasma source (DPS) manufactured by Applied Materials was used. The DPS chamber includes a vacuum chamber, a high-frequency power source (source power source) for generating plasma installed above the vacuum chamber, and a high-frequency power source (bias) for anisotropically irradiating ions to the substrate below the wafer. Power supply).
The frequency of the upper high frequency power source (source power source) was 2 MHz, and the frequency of the lower high frequency power source (bias power source) was 13.56 MHz. In addition, the cooling temperature of the wafer during etching was set to 20 ° C.

  The ICP power and bias power in the table indicate the power supplied to the source power supply and the bias power supply, respectively, and the pressure is a process pressure at the time of etching. The gas flow rate indicates the flow rate of the process gas that flows during etching, and is controlled by a mass flow controller. The processing time indicates the time when the etching process is performed.

  The silicon wafer subjected to the above treatment was washed by paddle with the first removal liquid for 20 seconds. For the example in which the second rinsing liquid is described in Table 3, after rinsing with the second rinsing liquid, the surplus film 2 is subsequently obtained by rotating the wafer at a rotational speed of 2000 rpm for 30 seconds. Was removed. This process corresponds to the above step E.

  Moreover, about the example in which the 2nd removal liquid was described in Table 3, it developed for 20 second using the 2nd removal liquid, and about the example in which the 3rd rinse liquid was described in Table 3, After rinsing with the third rinsing solution, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds to remove the pattern 1 to obtain a 1: 1 line and space resist pattern having a line width of 36 nm. This process corresponds to the above step D.

<Pattern formation: immersion exposure>
A resist pattern was obtained in the same manner as in <Pattern formation: Dry exposure> except that the pattern 1 formation method was changed to the following method (immersion exposure method). The obtained resist pattern was a 1: 1 line and space resist pattern having a line width of 22 nm.

(Immersion exposure method)
An ARC29SR (manufactured by Nissan Chemical Co., Inc.) for forming an organic antireflection film was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The resist composition (any one of Ar-1 to Ar-14) was applied thereon and baked at 90 ° C. for 60 seconds to form a resist film (film 1) having a thickness of 60 nm.
Next, an ArF excimer laser immersion scanner (XT1700i, NA1.20, Dipole, outer sigma 0.981 manufactured by ASML Co., Ltd.) was passed through this resist film through a 6% halftone mask having a line width of 44 nm and a 1: 1 line and space pattern. , Inner sigma 0.895, Y deflection). Ultra pure water was used as the immersion liquid. Thereafter, the exposed resist film was heated at 95 ° C. for 60 seconds and then cooled to room temperature. Next, development was performed by paddle development for 20 seconds using the first developer shown in Table 3 below. For examples in which the first rinse liquid was shown in Table 3, the first rinse shown in Table 3 below was used. Paddle was rinsed by using the liquid for 30 seconds to form pattern 1.

<Pattern bridge defect evaluation>
The pattern (spacer pattern) obtained above was observed with a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.), and the following three-stage evaluation was performed.
A: When a bridge is not observed between patterns B: When a bridge is slightly observed between patterns C: When a bridge is scattered between patterns <LWR evaluation of pattern>
In the obtained pattern, the line pattern is observed with a scanning microscope (S9280 manufactured by Hitachi, Ltd.), and the distance from the reference line where the edge should be is measured for 50 points in the range of 2 μm in the longitudinal direction of the line pattern, The standard deviation was calculated and 3σ was calculated. A smaller value indicates better performance.

  In Table 3 below, “Mw” in the “spacer agent” column indicates the molecular weight (mass of one molecule) when the spacer agent is S-1 to S-8 and S-15, and the spacer agent is S. In the case of -9 to S-14 and S-16, the weight average molecular weight is intended.

Abbreviations in Table 3 are as follows.
TMAH: Tetramethylammonium hydroxide aqueous solution (concentration: 2.38% by mass)
MIBC: 4-methyl-2-pentanol PGMEA: propylene glycol monomethyl ether acetate EL: ethyl lactate MAK: 2-heptanone organic solvent A: spacer agent S-1 described later at a ratio of 2% by mass with respect to butyl acetate Mixed solvent.

[Spacer agent]
The spacer agents used in Table 3 are shown below.

  In Table 3, multiple types having different molecular weights are used for S-10.

  In Table 3, the “ArF dry” column shows the evaluation of the pattern formed by the above <pattern formation: dry exposure>, and the “ArF liquid immersion” column is formed by the above <pattern formation: immersion exposure>. The evaluation of the pattern is shown.

As shown in Table 3, according to the pattern forming method of the present invention, a pattern with few defects can be obtained. In particular, when the molecular weight of the film forming component is 1000 or more, it was confirmed that a more excellent effect can be obtained. Further, as a solvent in the spacer forming composition, LWR was more excellent in a system having a small water content (a system in which only an organic solvent is used as a solvent).
On the other hand, in Comparative Examples 1 to 5 in which etching using cluster ions was not performed, the desired effect was not obtained.

Although the embodiments have been described above, the present invention is not limited to these embodiments. For example, pattern formation is also possible in the following modes (mode X and mode Y).
Aspect X: Aspect aspect Y in which negative development is carried out by adding about 1% by mass of a nitrogen-containing basic compound such as trioctylamine to the butyl acetate developer used in Step A of Examples 20 to 24 (EUV exposure mode): In the examples, the ArF excimer laser exposure was changed to EUV exposure. Further, as the resin in the resist composition, the above-mentioned “especially during EUV exposure or electron beam exposure, Embodiment using resin introduced as “resin that can be suitably used”.

(Preparation of spacer forming composition)
The components shown in Table 4 below are dissolved in the solvents shown in the same table to give a total solid content concentration of 4% by mass, and each is filtered through a filter having a pore size of 0.1 μm to form a spacer-forming composition (treating agents 1 to 23). ) Was prepared.

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

  V-13: Polyvinyl 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, trade name “Sokalan HP56 K”)

[Crosslinking component 1]
X-1: Ethylene glycol diglycidyl ether (2 epoxy groups, trade name: Epolite 40E, manufactured by Kyoeisha Chemical Co., Ltd.)
X-2: Trimethylolethane triglycidyl ether (3 epoxy groups, trade name: Epolite 100MF, manufactured by Kyoeisha Chemical Co., Ltd.)
X-3: Dimethylolpropane diglycidyl ether (2 epoxy groups, trade name: Epolite 1500NP, manufactured by Kyoeisha Chemical Co., Ltd.)
X-4: Pentaerythritol tetraglycidyl ether (4 epoxy groups, trade name: Denacol EX-411, manufactured by Nagase ChemteX Corporation)
X-5: Dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether (six oxetanyl groups)
X-6: Nikarak MX-750 (Nippon Carbite, product name)
X-7: Dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether

  X-9: Tetra (hydroxymethyl) glycoluril (Mitsui Cytec Co., Ltd., trade name “Cymel 1172”)

[Crosslinking component 2]
XII-1: Methoxymethylated melamine resin (trade name: Cymel 300, manufactured by Nippon Cytex Co., Ltd.)
XII-2: Methoxymethylated melamine resin (trade name: Cymel 325, manufactured by Nippon Cytex Co., Ltd.)

〔Additive〕
AD-1: Triethylamine

[Surfactant]
W-1: Megafuck F176 (manufactured by DIC Corporation) (fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)
W-4: PolyFox PF-6320 (made by OMNOVA) (fluorine-based)
W-5: PRISURF A210G (Daiichi Kogyo Seiyaku Co., Ltd.) (phosphate ester type)

  A pattern according to the same procedure as in Example 1 except that the spacer-forming composition (treatment agents 1 to 23) was used as the spacer-forming composition, and the baking temperature and time were changed as shown in Table 4. As a result of the formation, a pattern could be formed in any manner as in Example 1.

10 substrate 12 pattern 1
14 Membrane 2
16 Interaction membrane

Claims (10)

Forming a pattern 1 containing an organic substance on a substrate;
Forming a film 2 covering the pattern 1; and
And a step C of removing at least part of the pattern 1 by etching the film 2 with cluster ions to expose at least part of the pattern 1.   2. The pattern forming method according to claim 1, further comprising a step D of removing at least a part of the pattern 1 while leaving the film 2 after the step C. 3.   The step A includes a step of forming the film 1 on the substrate using an actinic ray-sensitive or radiation-sensitive resin composition, a step of irradiating the film 1 with an actinic ray or radiation, and a post-irradiation step. The pattern forming method according to claim 1, further comprising: developing the film 1 to form the pattern 1.   The pattern formation method according to claim 3, wherein the actinic ray-sensitive or radiation-sensitive resin composition is a composition containing a resin whose polarity is increased by the action of an acid.   The pattern forming method according to claim 3, wherein the development of the film 1 is performed using an alkaline aqueous solution.   The pattern forming method according to claim 1, wherein the step B includes a step of applying a composition used for forming the film 2 on the pattern 1.   The pattern formation method of Claim 6 whose composition used for formation of the said film | membrane 2 is a composition containing a film formation component and an organic solvent.   The pattern forming method according to claim 7, wherein the organic solvent includes at least one of an alcohol solvent and an ether solvent.   The pattern forming method according to claim 2, wherein the step D includes a step of removing at least a part of the pattern 1 with a treatment liquid containing an organic solvent.   The manufacturing method of an electronic device containing the pattern formation method of any one of Claims 1-9.