JP2019032349A - Patterning method, method for producing electronic device and resin composition for reverse pattern - Google Patents

Abstract

To provide a patterning method that can form a fine reverse pattern in which the occurrence of a bridge fault is prevented.SOLUTION: A patterning method has includes the steps of (a) applying an active ray-sensitive or radiation-sensitive resin composition containing a resin (A) that has its polarity increased by the action of an acid, to a substrate to form a first film 30, (b) exposing the first film 30, (c) patterning the exposed first film 3 by image development, to form a first pattern 30a, (d) applying a resin composition for reverse pattern to the first pattern, to form a second film 40, and (e) removing the first pattern 30a with a treatment liquid to pattern the second film, thereby forming a second pattern 40a having a reversed shape of the first. The resin composition for reverse pattern contains two or more resins, and at least two of the resins have different dissolution rates in the treatment liquid.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a pattern forming method, an electronic device manufacturing method, and a pattern reversal resin composition. More specifically, the present invention relates to a pattern forming method and an electronic device suitable for semiconductor manufacturing processes such as IC (Integrated Circuit), circuit boards such as liquid crystal and thermal head, and other photofabrication lithography processes. And a resin composition for pattern reversal.

  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. For example, in the positive chemical amplification method, first, a photoacid generator contained in an exposed portion is decomposed by light irradiation to generate an acid. The alkali-insoluble group contained in the actinic ray-sensitive or radiation-sensitive resin composition is changed to an alkali-soluble group by the catalytic action of the acid generated in the post exposure bake (PEB) process. . Thereafter, development is performed using, for example, an alkaline solution. Thereby, an exposed part is removed and a desired pattern is obtained.

  In the above method, various alkali developers have been proposed. For example, as this alkaline developer, a 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) aqueous alkaline developer is generally used.

  To reduce the size of semiconductor elements, the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. 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.

  Under such circumstances, various techniques relating to a method for forming a positive pattern have been proposed. In addition to the current mainstream positive type, a negative type developer, that is, a negative pattern forming method using a developer containing an organic solvent (hereinafter also referred to as “organic developer”) has been developed. ing. This is because, in the manufacture of semiconductor elements and the like, there is a demand for forming patterns having various shapes such as lines, trenches, and holes, but there are patterns that are difficult to form by the current positive chemical amplification method.

  Recently, various techniques for reversing a negative pattern into a positive pattern have been proposed as techniques for resolving fine patterns of various shapes. As one of such technologies, a pattern reversal resin composition is applied on a negative resist pattern formed by development using an organic developer to form a pattern reversal film, and then subjected to alkali development. There is a technique of forming a pattern in which an image of the negative resist pattern is inverted by removing the negative resist pattern and patterning a pattern inversion film (see, for example, Patent Documents 1 and 2).

JP2015-125387A JP 2014-106298 A

  As a result of intensive studies by the present inventors, it has been found that when a fine pattern is formed using the above-described pattern inversion technique, a problem of a bridge defect is likely to occur and there is room for further improvement.

  This invention is developed in view of the said situation, and makes it a subject to provide the pattern formation method which can form the fine inversion pattern by which generation | occurrence | production of the bridge defect was suppressed. Moreover, this invention makes it a subject to provide the resin composition for pattern inversion useful for the manufacturing method of an electronic device containing this pattern formation method, and this pattern formation method.

In one aspect, the present invention is as follows.
[1]
(A) a step of applying an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) whose polarity is increased by the action of an acid onto a substrate to form a first film;
(B) exposing the first film;
(C) patterning the exposed first film by development to form a first pattern;
(D) applying a resin composition for pattern reversal on the first pattern to form a second film; and
(E) A pattern forming method including a step of patterning a second film by removing a first pattern using a treatment liquid and forming a second pattern in which the shape of the first pattern is reversed. ,
The pattern reversal resin composition contains two or more kinds of resins, and at least two kinds of the resins have different dissolution rates in the treatment liquid.

[2]
The pattern forming method according to [1], wherein the developing step (c) is a step of forming a negative pattern by developing the first film using a developer containing an organic solvent.
[3]
The pattern forming method according to [1] or [2], wherein the treatment liquid is an alkaline solution.

[4]
Among at least two types of resins having different dissolution rates in the treatment liquid, the resin contains at least one alkali-soluble resin as a resin having a higher dissolution rate in the treatment liquid and has a lower dissolution rate in the treatment liquid. The pattern forming method according to any one of [1] to [3], which contains at least one alkali-insoluble resin.

[5]
Of at least two resins having different dissolution rates in the treatment liquid, at least one resin having a higher dissolution rate in the treatment liquid is contained in fluorine atoms, silicon atoms, and side chain portions of the resin. The pattern forming method according to any one of [1] to [4], which has any one or more of CH ₃ partial structures.

[6]
The pattern formation method of any one of Claims 1-5 including the process of baking at least once between a image development process (c) and a pattern inversion process (e).

[7]
Baking process between the development process (c) and the second film forming process (d) and between the second film forming process (d) and the pattern reversal process (e). The pattern forming method according to [6], including:

[8]
The pattern forming method according to any one of [1] to [7], wherein the resin composition for pattern reversal further contains a thermal acid generator.

[9]
The manufacturing method of an electronic device containing the pattern formation method of any one of [1]-[8].

[10]
A pattern reversal resin composition used in a pattern forming method for removing a resist pattern with an alkaline solution to obtain a reversal pattern for the resist pattern, the pattern comprising two types of resins having different dissolution rates in the alkaline solution Inversion resin composition.

  According to the present invention, it is possible to provide a pattern forming method capable of forming a fine reversal pattern in which generation of bridge defects is suppressed. In addition, according to the present invention, it is possible to provide an electronic device manufacturing method including this pattern forming method and a pattern reversal resin composition useful for this pattern forming method.

1A to 1E are schematic sectional views for explaining a pattern forming method according to an embodiment of the present invention. FIG. 2A is an image observed by a scanning electron microscope of the resist pattern (first pattern) before inversion. FIG. 2B is an image observed by a scanning electron microscope of the reverse pattern (second pattern) obtained by the pattern forming method according to the embodiment of the present invention. FIG. 2C is a reversal pattern obtained by the pattern formation method according to the comparative example, and a pattern formation method using a pattern reversal resin composition containing only one kind of resin that does not dissolve in the treatment liquid as a resin component. It is an observation image by the scanning electron microscope of the obtained inversion pattern.

  In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  In addition, the term “active light” or “radiation” in the present specification refers to, for example, an emission line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultra violet (EUV) ray, an X ray or an electron beam ( Electron Beam (EB). In the present invention, “light” means actinic rays or radiation.

In addition, the term “exposure” in the present specification is not limited to exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays and EUV light, but also with particle beams such as electron beams and ion beams, unless otherwise specified. Drawing is also included in the exposure.
Hereinafter, embodiments of the present invention will be described in detail.

The pattern forming method of the present invention comprises:
(A) a step of applying an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) whose polarity is increased by the action of an acid onto a substrate to form a first film;
(B) exposing the first film;
(C) patterning the exposed first film by development to form a first pattern;
(D) applying a resin composition for pattern reversal on the first pattern to form a second film; and
(E) The process of patterning a 2nd film | membrane by removing a 1st pattern using a process liquid, and forming the 2nd pattern in which the shape of the 1st pattern was reversed is included.

  And the pattern formation method of this invention contains 2 or more types of resin as said resin composition for pattern inversion, and at least 2 types of resin in it has the composition from which the melt | dissolution rate with respect to the said process liquid differs mutually. One of the features is the use.

  As a result of intensive studies by the present inventors, in the conventional pattern reversal technique including the steps (a) to (e), a bridge defect is likely to occur, and the cause thereof is a film for pattern reversal that is the second film. It has been found that the surface layer portion of the layer remains due to insufficient solubility in the treatment liquid used for removing (peeling) the first pattern.

  And this invention uses as a main component of the pattern reversal resin composition which forms the film for pattern reversal which is a 2nd film | membrane, combining and using at least 2 type of resin from which the melt | dissolution rate with respect to the said process liquid mutually differs. The present invention has been completed based on the knowledge found by the present inventors that it is effective in suppressing bridge defects in the pattern inversion technique.

  Hereinafter, the pattern forming method of the present invention will be described with reference to FIG. 1, and then the pattern reversal resin composition, the actinic ray-sensitive or radiation-sensitive resin composition will be described in this order.

<< Pattern Forming Method >>
The pattern forming method of the present invention includes a step (a) for forming a first film, an exposure step (b), a developing step (c), and a step (d) for forming a second film, as will be described below. And a pattern inversion step (e). In one embodiment, the pattern forming method of the present invention preferably includes at least one baking step between the development step (c) and the pattern reversal step (e), and in another embodiment, the development step (c) A baking step is preferably included between the step (d) of forming the second film and / or between the step (d) of forming the second film and the pattern inversion step (e).

<Step (a) of Forming First Film>
In the pattern forming method of the present invention, an actinic ray-sensitive or radiation-sensitive resin composition is applied onto a substrate and a first film (hereinafter referred to as “activatable light-sensitive or radiation-sensitive film” or “resist film”) is used. Step (a).

  More specifically, as shown in FIG. 1 (a), a processed layer 20 is usually formed on the substrate 10, and the actinic ray-sensitive or radiation-sensitive resin composition is formed on the processed layer 20. As a result, an actinic ray-sensitive or radiation-sensitive film (first film) 30 is formed on the work layer 20.

  Application of the actinic ray-sensitive or radiation-sensitive resin composition on the substrate can be performed by an appropriate application method such as a spin coater.

  The film thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably adjusted in the range of 10 to 500 nm, more preferably in the range of 10 to 200 nm, and still more preferably in the range of 10 to 80 nm. To do. When the actinic ray-sensitive or radiation-sensitive resin composition is applied by a spinner, the rotation speed is usually 500 to 3000 rpm, preferably 800 to 2000 rpm, more preferably 1000 to 1500 rpm.

  As the layer to be processed 20, a substrate (eg, silicon, silicon dioxide coating) used for manufacturing an integrated circuit element can be used.

  Moreover, the to-be-processed layer 20 may be equipped with the inorganic or organic anti-reflective film as needed. As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

<Bake process (1)>
In one embodiment of the present invention, the actinic ray-sensitive or radiation-sensitive film is preferably dried, and preferably heated (prebaked) (PB) at the drying stage.

The heating (PB) temperature is preferably 60 to 200 ° C, more preferably 80 to 150 ° C, and still more preferably 90 to 140 ° C.
The heating (PB) time is not particularly limited, but is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating (PB) can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

<Exposure step (b)>
The pattern formation method of this invention includes the process (b) which exposes the actinic-ray-sensitive or radiation-sensitive film | membrane (1st film | membrane) 30 after a process (a), as shown in FIG.1 (b). .

In the present invention, the wavelength of the light source used in the exposure apparatus is not limited, but infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultra violet (EUV) light, X-ray, electron beam (electron beam). EB) and the like, preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 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 light (13 nm), electron beam (EB), etc., preferably KrF excimer laser, ArF excimer laser, X-ray, EUV light or electron beam, ArF excimer Laser, electron beam, X-ray or EUV light is more preferable.

  When extreme ultraviolet (EUV) light or the like is used as an exposure source, it is preferable to irradiate the formed film with EUV light (around 13 nm) through a predetermined mask. In irradiation with an electron beam (EB), drawing (direct drawing) without using a mask is common.

  The actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has a refractive index that is higher than that of air between the film and the lens when irradiated with actinic rays or radiation. Exposure (immersion exposure) may be performed by filling a high liquid (immersion medium). Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.

  The immersion liquid used for the immersion exposure will be described below.

  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 resist film. In addition, it is preferable to use water from the viewpoint of easy availability and ease of handling.

  Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, the surface tension of the water is decreased and the surface activity is increased, so that the resist film on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element can be ignored. An additive (liquid) may be added in a small proportion. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes 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 impurity whose refractive index is significantly different from that of water is mixed, the optical image projected on the resist film is distorted, so that 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 water is desirably 18.3 MΩcm or more, the TOC (Total Organic Carbon) concentration is desirably 20 ppb (parts per billion) or less, and deaeration treatment is performed. desirable.
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.

  An immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) may be provided between the film of the composition of the present invention and the immersion liquid so that the film does not directly contact the immersion liquid. Good. The functions necessary for the top coat are suitability for application to the upper layer portion of the composition film and poor solubility of the immersion liquid. It is preferable that the top coat is not mixed with the composition film and can be uniformly applied to the upper layer of the composition film.

  Specific examples of the topcoat include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, fluorine-containing polymers, and the like. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

  When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed at the same time as the film development processing step, it is preferable that the peeling step can be performed with a developer containing an organic solvent.

  The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. When water is used as the immersion liquid, the top coat is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

  The topcoat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Further, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

<Bake process (2)>
In the pattern forming method of the present invention, it is preferable to perform post exposure bake (PEB) after the exposure step (b) described above and before the development step (c) described later.
The heating (PEB) temperature is preferably 60 to 150 ° C, more preferably 80 to 150 ° C, and still more preferably 90 to 140 ° C.
The time for heating (PEB) is not particularly limited, but is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating (PEB) can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
PEB promotes the reaction of the exposed area and improves the sensitivity and pattern profile.

<Development step (c)>
In the pattern forming method of the present invention, after the exposure step (b), the exposed actinic ray-sensitive or radiation-sensitive film (first film) is developed with a developer and patterned (c). including. By this development, a first pattern including a space portion (concave portion) from which a part of the actinic ray-sensitive or radiation-sensitive film is removed and a remaining film portion (convex portion) that is not removed is formed.

  The developer that can be used in the developer step (c) may be a developer containing an organic solvent (hereinafter also referred to as “organic developer”) or an alkali developer, and is formed. The first pattern may be a negative pattern or a positive pattern.

  Preferred examples of the developing step (c) include a step of forming a negative pattern using a developer containing an organic solvent and a step of forming a positive pattern using an alkaline developer.

  FIG. 1C shows a process of forming a negative pattern using an organic developer, and a part of the actinic ray-sensitive or radiation-sensitive film 30 is removed by organic solvent development. A negative pattern (first pattern) 30a including a space (concave portion) 31a and a remaining film portion (convex portion) 31b that is not removed by organic solvent development is formed.

In one embodiment of the present invention, the thickness of the first pattern is preferably in the range of 10 to 500 nm, more preferably in the range of 10 to 200 nm, and even more preferably in the range of 10 to 80 nm.
[Organic developer]
Vapor pressure of organic developer that can be used when step (c) is a step of forming a negative pattern as the first pattern by patterning by development using an organic developer (in the case of a mixed solvent) (Vapor pressure as a whole) at 20 ° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. It improves.

  Various organic solvents are widely used as organic solvents used in organic developers. For example, ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, etc. These solvents can be used.

  In the present invention, the ester solvent is a solvent having an ester group in the molecule, the ketone solvent is a solvent having a ketone group in the molecule, and the alcohol solvent is alcoholic in the molecule. It is a solvent having a hydroxyl group, an amide solvent is a solvent having an amide group in the molecule, and an ether solvent is a solvent having an ether bond in the molecule. Among these, there is a solvent having a plurality of types of the above functional groups in one molecule. In that case, it corresponds to any solvent type including the functional group of the solvent. For example, diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification. Further, the hydrocarbon solvent is a hydrocarbon solvent having no substituent.

  In particular, a developer containing at least one kind of solvent selected from ketone solvents, ester solvents, alcohol solvents and ether solvents is preferable.

  Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, pentyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy- 2-acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monophenyl ether ace , Diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl Acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl Ru-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, Butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, Examples include ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like. it can.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Examples include phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, and γ-butyrolactone.

  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, 2-hexyl alcohol, alcohols such as n-heptyl alcohol, n-octyl alcohol, n-decanol, 3-methoxy-1-butanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether Contains hydroxyl groups such as methoxymethyl butanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether Examples include glycol ether solvents. Among these, it is preferable to use a glycol ether solvent.

  Examples of ether solvents include glycol ether solvents containing hydroxyl groups, glycol ether solvents that do not contain hydroxyl groups such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, anisole, and phenetole. Aromatic ether solvents, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like. Preferably, an glycol ether solvent or an aromatic ether solvent such as anisole is used.

  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 used.

  Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluoroheptane. Aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc. Can be mentioned. Among these, aromatic hydrocarbon solvents are preferable.

  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 achieve the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, preferably 5% by mass or less, and 1% by mass or less. More preferably, it is most preferably substantially free of moisture.

  The concentration (content) of the organic solvent in the organic developer (total in the case of mixing) is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% with respect to the total amount of the developer. It is 90 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less. Particularly preferred is a case consisting essentially of an organic solvent. In addition, the case where it consists only of an organic solvent includes the case where a trace amount surfactant, antioxidant, stabilizer, an antifoamer, etc. are contained.

  Of the above solvents, it is more preferable to contain one or more selected from the group consisting of butyl acetate, pentyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, and anisole.

-Surfactant The organic developer may contain an appropriate amount of a surfactant as required.

  As the surfactant, the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive resin composition described later can be used.

  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 development step (c) is a step of forming a positive pattern as a first pattern by patterning by development using an alkaline developer, and an alkaline solution is used as a treatment solution in the pattern inversion step (e) described later. When using, the process which solubilizes the positive pattern which is a 1st pattern in an alkaline solution is needed.

  Examples of the solubilization treatment include a means for heating the positive pattern which is the first pattern obtained in the development step (c). A group (hereinafter referred to as “acid decomposition”), which is generated in the exposure step (c), which remains slightly in the positive pattern by heating, is contained in the resin (A) described later and whose polarity is increased by the action of the acid. Since the decomposition reaction of the functional group is also advanced, the solubility of the positive pattern in the alkaline solution used in the pattern inversion step (e) is improved. This heat treatment corresponds to “post-development baking” described as a baking step (3) described later and / or “post-application baking” described as a baking step (4).

  As another solubilization treatment, there is a means for exposing the positive pattern, which is the first pattern obtained in the development step (c), and then preferably heating. Since the acid generator that can be contained in the positive pattern is decomposed by exposure and the decomposition reaction of the acid-decomposable group contained in the resin (A) described later proceeds, the alkaline solution used in the pattern inversion step (e) The solubility of the positive pattern with respect to is improved. This heat treatment corresponds to “baking after development” and / or “baking after application”.

  As another solubilization treatment, in the second film formation step (d) described later, a pattern reversal film (second film) is formed by using a composition containing a thermal acid generator as the pattern reversal resin composition. The film may be heated after the film is formed. As a result, the acid generator that can be contained in the positive pattern is decomposed, and the decomposition reaction of the acid-decomposable group contained in the resin (A) described later proceeds, so that the alkaline solution used in the pattern inversion step (e) The solubility of the positive pattern with respect to is improved. This heat treatment corresponds to “post-application baking” described as a baking step (4) described later.

[Alkali developer]
Examples of the alkaline developer that can be used when the step (c) is a step of forming a positive pattern as the first pattern by patterning by development using an alkaline developer include, for example, sodium hydroxide, hydroxide Inorganic alkalis such as potassium, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, triethylamine, Tertiary amines such as methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, cyclic amines such as pyrrole and pihelidine, etc. Arca It can be used sex solution.

Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution. As the surfactant, the same surfactants that can be added in the organic developer can be used.
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.
In one embodiment of the present invention, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) is particularly preferable as the alkaline developer.

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

  The development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is usually 10 seconds to 300 seconds. Preferably, it is 20 seconds to 120 seconds.

  The temperature of the developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C.

<Rinse process (1)>
The pattern forming method of the present invention may include a step of washing with a rinsing liquid after the developing step (c).

[Rinse solution]
The rinsing solution used in the rinsing step after the step of developing with an organic developer 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 vapor pressure of the rinse liquid used after development (the vapor pressure as a whole in the case of a mixed 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. It is most preferably 12 kPa or more and 3 kPa or less. 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.

  As the rinsing liquid, various organic solvents are used. At least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents or It is preferable to use a rinse solution containing water.

  More preferably, after the development, a step of washing with a rinse solution containing at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent or a hydrocarbon solvent. Do. Even more preferably, after the development, a washing step is performed using a rinse solution containing an alcohol solvent, a hydrocarbon solvent, or a ketone solvent.

  Particularly preferably, a rinse liquid containing at least one selected from the group of monohydric alcohols and hydrocarbon solvents is used.

  Here, examples of the monohydric alcohol used in the rinsing step after the organic solvent development include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, 3- Methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3 -Heptanol, 3-octanol, 4-octanol, 3-methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2- Pentanol, 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentano 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dityl-2-hexal, 6 -Methyl-2-heptanol, 7-methyl-2-octanol, 8-methyl-2-nonal, 9-methyl-2-decanol, etc. can be used, preferably 1-hexanol, 2-hexanol, 1- Pentanol, 3-methyl-1-butanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, most Preferably, it is 1-hexanol or 4-methyl-2-pentanol.

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

  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.

  More preferably, the rinse liquid contains one or more selected from the group consisting of 1-hexanol, 4-methyl-2-pentanol (MIBC), decane, undecane, and diisobutyl ketone.

  A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above. The solvent may be mixed with water, but the water content in the rinsing liquid is usually 60% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. is there. A favorable rinse characteristic can be acquired by making a moisture content into 60 mass% or less.

  An appropriate amount of a surfactant can be contained in the rinse liquid.

  As the surfactant, the same surfactants used in the actinic ray-sensitive or radiation-sensitive resin composition described later can be used, and the amount used is usually 0 with respect to the total amount of the rinsing liquid. 0.001 to 5 mass%, preferably 0.005 to 2 mass%, more preferably 0.01 to 0.5 mass%.

  As the rinsing solution used in the rinsing step after the step of developing with an alkaline developer, pure water can be used, and an appropriate amount of a surfactant can be added.

[Rinse method]
In the rinsing step, the developed wafer is cleaned using the rinsing liquid.

  The method of the cleaning process is not particularly limited. For example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary discharge 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 these, a cleaning process is performed by a rotary discharge 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.

  The rinsing time is not particularly limited, but is usually 10 seconds to 300 seconds. It is preferably 10 seconds to 180 seconds, and most preferably 20 seconds to 120 seconds.

  The temperature of the rinse liquid is preferably 0 ° C. to 50 ° C., more preferably 15 ° C. to 35 ° C.

  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.

  Furthermore, after the development processing, the rinsing processing or the processing with the supercritical fluid, a heat processing can be performed in order to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 ° C to 160 ° C. The heating temperature is preferably 50 ° C. or higher and 150 ° C. or lower, and most preferably 50 ° C. or higher and 110 ° C. or lower. The heating time is not particularly limited as long as a good resist pattern is obtained, but is usually 15 seconds to 300 seconds, and preferably 15 to 180 seconds.

<Bake process (3)>
In one embodiment, the pattern forming method of the present invention includes a baking step (hereinafter also referred to as “post-development baking”) after the development step (c) described above (after the rinse step when a rinse step is included). It is preferable to include. Baking after development can be insolubilized in the solvent contained in the image reversal resin composition applied in the next step (d). In addition, the post-development baking causes a decomposition reaction of the group whose polarity is increased by the action of the acid in the resin (A) contained in the first pattern, and the processing liquid used in the pattern reversal step (e) described later. It becomes possible to improve the solubility with respect to.

  The heating temperature is preferably 80 to 300 ° C, more preferably 90 to 300 ° C, still more preferably 100 to 250 ° C, and particularly preferably 150 to 210 ° C.

  The heating time is not particularly limited, but is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.

  In addition, the developing solution or the rinsing solution remaining between the patterns and inside the patterns can be removed by this heating step.

<Step (d) of Forming Second Film (Pattern for Pattern Reversal)>
In the pattern forming method of the present invention, the resin composition for pattern reversal is applied onto the first pattern obtained by the developing step (c), and the second film (pattern reversal film) shown in FIG. ) 40 is formed. By this step, as shown in FIG. 1D, the resin composition for pattern reversal is embedded in the recesses 31a of the first pattern.

  The coating method is not particularly limited, and the coating is performed by an appropriate coating method such as a spin coater.

  The film thickness of the pattern inversion film (second film) is not particularly limited, but is preferably in the range of 10 to 500 nm, more preferably in the range of 10 to 200 nm, and still more preferably in the range of 10 to 80 nm. adjust. Here, the film thickness of the pattern reversal film means the thickness from the bottom surface (surface of the layer 20 to be processed) of the space (recessed portion) 31a of the first pattern 30a to the surface of the pattern reversal film 40.

  In one embodiment of the present invention, the film thickness (t1) of the first pattern and the film thickness (t2) of the pattern inversion film (second film) preferably satisfy the following relationship. That is, t2 / t1 ≦ 2 is preferable, t2 / t1 ≦ 1.5 is more preferable, and t2 / t1 ≦ 1 is still more preferable.

<Bake process (4)>
In one form, the pattern forming method of the present invention preferably includes a baking step after the step (d) of forming the second film. The bake after the step (d) (hereinafter also referred to as “post-apply bake”) is the resin (A) contained in the first pattern, similar to the post-development bake after the development step (c) described above. It is preferable because the decomposition reaction of the group whose polarity increases by the action of the acid therein proceeds and the solubility in the treatment liquid used in the step (e) for forming the next second pattern can be improved. Further, post-application baking after the step (d) is preferable because the film for pattern reversal (second film) can be heated to improve the flatness.

The heating temperature is preferably 80 to 300 ° C, more preferably 90 to 300 ° C, still more preferably 100 to 250 ° C, and particularly preferably 150 to 210 ° C.
The heating time is not particularly limited, but is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed using a hot plate or the like.

<Pattern reversal process (e)>
In the pattern forming method of the present invention, the second film is patterned by removing the remaining film portion in the first pattern using the treatment liquid, and the remaining film portion and the space portion are reversed with respect to the first pattern. A step (e) of forming a second pattern (reversal pattern) (hereinafter also referred to as a “pattern reversal step”).

  Referring to FIG. 1, in the pattern inversion step (e), the remaining film portion (31b) of the first pattern 30 (a) shown in FIG. The film 40 is patterned to form a second pattern (40a) shown in FIG. 1 (e) in which the remaining film portion and the space portion are inverted with respect to the first pattern 30a.

  As will be described later, the pattern reversal film (second film) contains two types of resins (resin (XA1) and resin (XA2)) having different dissolution rates in the treatment liquid. In the pattern reversal step (e), the first pattern is removed by the treatment liquid, and the resin (XA1) contained in the surface layer portion of the pattern reversal film and having a higher dissolution rate with respect to the treatment liquid is dissolved in the treatment liquid. This contributes to the suppression of bridge defects.

  For this reason, the treatment liquid that can be used in the pattern reversal step (e) (hereinafter also referred to as “the treatment liquid of the present invention”) is the first pattern and the treatment liquid contained in the pattern reversal film. A treatment solution that dissolves the resin (XA1) having higher solubility is used.

  An example of such a treatment liquid is an alkaline solution. Examples of the alkaline solution that can be used as the treatment liquid include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and first amines such as ethylamine and n-propylamine. Secondary amines such as amines, diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy And alkaline aqueous solutions of quaternary ammonium salts such as pyrrole and cyclic amines such as pyrrole and pihelidine.

  Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline solution.

  The alkali concentration of the alkaline solution is usually 0.1 to 20% by mass, preferably 1 to 10% by mass. From the viewpoint of availability, 2.38% by mass is preferable.

  In one embodiment of the present invention, the alkaline solution is preferably a 2.38 mass% aqueous solution of tetramethylammonium hydroxide.

The pH of the alkaline solution is usually 10.0 to 15.0.
The processing time (alkali development time) when an alkaline solution is used as the processing solution of the present invention is not particularly limited, and is usually 10 seconds to 300 seconds, and preferably 20 seconds to 120 seconds.

  The temperature of the alkaline solution is preferably 0 ° C to 50 ° C, more preferably 15 ° C to 35 ° C.

<Rinse process (2)>
After the pattern inversion step (e), a rinsing process can be performed. As the rinse liquid in the rinse treatment performed after the removal of the first pattern using the alkali treatment, pure water is preferable, and an appropriate amount of a surfactant can be added and used.

<Bake process (5)>
Furthermore, after the pattern reversal process or the rinsing process, a process of removing the remaining developer or rinsing liquid by heating can be performed. The heating temperature is not particularly limited as long as a good pattern is obtained, and is usually 40 ° C to 160 ° C. The heating temperature is preferably 50 ° C. or higher and 150 ° C. or lower, and most preferably 50 ° C. or higher and 110 ° C. or lower. The heating time is not particularly limited as long as a good pattern is obtained, but is usually 15 seconds to 300 seconds, and preferably 15 to 180 seconds.

<< Pattern Reversal Resin Composition >>
The resin composition for pattern reversal contains at least two kinds of resins having different dissolution rates in the treatment liquid of the present invention used in the pattern reversal step (e) as a resin that is an organic compound having film forming ability. . The resin composition for pattern reversal may contain an organic solvent, a thermal acid generator, a surfactant, and the like as components other than the resin. Hereinafter, each component will be described.

<Resin>
The resin composition for pattern reversal contains a resin component (XA) as an organic compound having film-forming ability, and at least two resins having different dissolution rates in the treatment liquid of the present invention are used as the resin component (XA). contains. Here, a resin having a higher dissolution rate in the treatment liquid of the present invention is referred to as “resin (XA1)”, and a resin having a lower dissolution rate in the treatment liquid is referred to as “resin (XA2)”.

In the pattern reversal step (e), as described above, the first pattern is removed by the treatment liquid, and the resin (XA1) contained in the surface layer portion of the pattern reversal film and having a higher dissolution rate with respect to the treatment liquid. It dissolves in the processing solution, which contributes to the suppression of bridge defects. From this viewpoint, the resin (XA1) preferably has a property of being unevenly distributed in the surface layer portion of the film (hereinafter also referred to as “unevenly distributed”). In one embodiment of the present invention, “fluorine atom”, “silicon It preferably has at least one of “atom” and “CH ₃ partial structure contained in the side chain portion of the resin” (hereinafter also simply referred to as “CH ₃ partial structure”).

  When an alkaline solution is used as the treatment liquid of the present invention, the resin (XA1) and the resin (XA2) have a higher dissolution rate for the alkaline solution in the resin (XA1) than in the resin (XA2).

  Here, the dissolution rate of the resin (XA1) and the resin (XA2) in the alkaline solution was 23% C. TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%) with respect to the resin (XA1) or the resin ( XA2) is defined as a rate (nm / sec) at which the film thickness decreases when a resin film made only of XA2) is formed.

  In one embodiment of the present invention, the dissolution rate of each of the resin (XA1) and the resin (XA2) in the alkaline solution is preferably at least twice as high as the dissolution rate of the resin (XA2). It is more preferably at least twice as large, and even more preferably at least 100 times as large.

In one embodiment of the present invention, the resin (XA1) is preferably an alkali-soluble resin, and the resin (XA2) is preferably an alkali-insoluble resin.
Hereinafter, the resin (XA1) and the resin (XA2) will be described in more detail.

[Resin (XA1)]
The resin (XA1) having a higher dissolution rate with respect to the treatment liquid of the present invention is made of “fluorine atom”, “silicon atom”, and “CH contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer portion. It is preferable to have any one or more of “ _three partial structures”.

  When the resin (XA1) has at least one of a fluorine atom and a silicon atom, the fluorine atom and / or the silicon atom may be contained in the main chain of the resin or may be contained in the side chain. .

  When the resin (XA1) contains a fluorine atom, it 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 as a partial structure having a fluorine atom. Is preferred.

  The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, You may have the substituent of.

  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 another substituent.

  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 the aryl group may further have another substituent.

  As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present 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). Provided that 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 a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. (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 a fluoroalkyl group (preferably having 1 to 4 carbon atoms), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. When R ₆₂ and _{R 63} is a perfluoroalkyl _group, it is preferred that _{R 64} is a hydrogen atom. 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.

  Suitable examples of the repeating unit having a fluorine atom include those shown below.

In formulas (C-Ia) to (C-Id), R ₁₀ and R ₁₁ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. .

W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

  In addition to these, the resin (XA1) may have a unit as shown below as a repeating unit having a fluorine atom.

In formulas (C-II) and (C-III), R _{4 to} R ₇ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. .

However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.

W ₂ represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or alkyl), —NHSO ₂ — or a divalent linking group in which a plurality of these are combined.

  Q represents an alicyclic structure. The alicyclic structure may have a substituent, may be monocyclic, may be polycyclic, and may be bridged in the case of polycyclic. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, dicyclopentyl group. , Tricyclodecanyl group, tetocyclododecyl group and the like. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. Particularly preferred examples of Q include a norbornyl group, a tricyclodecanyl group, a tetocyclododecyl group, and the like.

  Resin (XA1) may contain a silicon atom.

  The partial structure having a silicon atom preferably has 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. The divalent linking group includes an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, or a group of two or more groups selected from the group consisting of a ureylene bond. A combination is mentioned.

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

  The repeating unit having at least either a fluorine atom or a silicon atom is preferably a (meth) acrylate repeating unit.

  Specific examples of the repeating unit having at least one of a fluorine atom and a silicon atom include the repeating unit disclosed in paragraph 0576 of US Publication No. 2012/0135348, but the present invention is not limited thereto. Is not to be done.

Further, as described above, the resin (XA1) also preferably includes a CH ₃ partial structure in the side chain portion. For the reason that the effect of the present invention is more excellent, the resin (XA1) preferably contains a repeating unit having at least one CH ₃ partial structure in the side chain portion, and has at least two CH ₃ partial structures in the side chain portion. It is more preferable to include a repeating unit having, and it is further preferable to include a repeating unit having at least three CH ₃ partial structures in the side chain portion.

Here, the CH ₃ partial structure possessed by the side chain moiety in the resin (XA1) (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 (XA1) (for example, an α-methyl group of a repeating unit having a methacrylic acid structure) causes the uneven distribution of the surface of the resin (XA1) by 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 (XA1) 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 resin (XA1) more preferably has a repeating unit represented by the following general formula (II) as a repeating unit having a CH ₃ partial structure in the side chain portion.

  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 an organic group.

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. Specific examples of preferable alkyl groups include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5- Examples thereof include a dimethyl-3-heptyl group and 2,3,5,7-tetramethyl-4-heptyl group. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 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 is there.

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. Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and tricyclodecanyl group. More 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 isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2-methyl-3-butyl. Group, 3-hexyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl 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, Examples include 3,5-dimethylcyclohexyl group, 3,5-ditert-butylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group, and isobornyl group. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2,3-dimethyl-2-butyl group, a 2-methyl-3-pentyl group, a 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-butylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group and 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.

  When the resin (XA1) has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, based on the weight average molecular weight of the resin (XA1). preferable. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% with respect to all the repeating units in resin (XA1), and it is more preferable that it is 30-100 mol%.

  When the resin (XA1) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the weight average molecular weight of the resin (XA1). preferable. Moreover, it is preferable that it is 10-90 mol% with respect to all the repeating units of resin (XA1), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-80 mol%.

When the resin (XA1) has “CH ₃ partial structure contained in the side chain portion of the resin”, the repeating unit having the CH ₃ partial structure contained in the side chain portion of the resin is included in all the repeating units in the resin. On the other hand, it is preferably 10 to 100 mol%, more preferably 30 to 100 mol%.

  When an alkaline solution is used as the treatment liquid of the present invention, the resin (XA1) is preferably an alkali-soluble resin from the viewpoint of suppressing bridge defects. Here, the alkali-soluble resin means a resin having a dissolution rate in an alkaline solution as defined above of 1 nm / sec or more. The dissolution rate of the alkali-soluble resin (AX1) in the alkaline solution is preferably 10 nm / sec or more, more preferably 100 nm / sec or more, and further preferably 1000 nm / sec or more.

  The resin (XA1) preferably has a repeating unit (b) having at least one group selected from the group consisting of the following (x) to (z).

(X) Alkali-soluble group (y) A group that decomposes by the action of an alkali developer and increases the solubility in an alkali developer (hereinafter also referred to as a polar conversion group).
(Z) a group that is decomposed by the action of an acid to increase the solubility in an alkali developer. In the following, a group selected from the group consisting of (x) to (z) above is a group consisting of “(x) to (z)”. May be referred to as “an alkali-soluble group selected from”.

  Examples of the repeating unit (b) include the following types.

A repeating unit (b ′) having at least one of a fluorine atom and a silicon atom and at least one group selected from the group consisting of the above (x) to (z) on one side chain
A repeating unit (b *) having at least one group selected from the group consisting of (x) to (z) and having no fluorine atom and no silicon atom
A fluorine atom and silicon on one side chain having at least one group selected from the group consisting of (x) to (z) and different from the side chain in the same repeating unit Repeating unit (b ″) having at least one of atoms
Examples of the alkali-soluble group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, 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 (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.

  Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

  As the repeating unit (bx) having an alkali-soluble group (x), a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a linking group is used. Examples include repeating units in which an alkali-soluble group is bonded to the main chain of the resin, and a polymerization initiator or chain transfer agent having an alkali-soluble group can also be introduced at the end of the polymer chain during polymerization. In any case, it is preferable.

  When the repeating unit (bx) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit (bx) corresponds to the repeating unit (b ′) or (b ″)), the repeating unit (bx) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (bx) is the same as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the above general formulas (CS-1) to (CS-3) can be exemplified.

  As for the content rate of the repeating unit (bx) which has an alkali-soluble group (x), 10-100 mol% is preferable with respect to all the repeating units in resin (XA1), More preferably, it is 30-100 mol%, More preferably, it is 50- 100 mol%.

  Specific examples of the repeating unit (bx) having an alkali-soluble group (x) include the repeating unit disclosed in paragraph 0595 of US Published Patent Application 2012/0135348, but the present invention is not limited thereto. Is not to be done.

Examples of the polar conversion group (y) include a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC (O) —), an acid imide group (—NHCONH—), A carboxylic acid thioester group (—COS—), a carbonic acid ester group (—OC (O) O—), a sulfate ester group (—OSO ₂ O—), a sulfonic acid ester group (—SO ₂ O—), and the like. A lactone group is preferred.

  The polarity converting group (y) is, for example, introduced into the side chain of the resin by being included in a repeating unit of acrylic acid ester or methacrylic acid ester, or a polymerization initiator or chain having the polarity converting group (y). Any form in which a transfer agent is introduced at the end of the polymer chain using the polymerization is preferred.

  Specific examples of the repeating unit (by) having a polar conversion group (y) include a repeating unit having a lactone structure represented by formulas (KA-1-1) to (KA-1-17) described later. Can do.

  Furthermore, the repeating unit (by) having the polarity converting group (y) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, the repeating unit (b ′) or (b ″)). The resin having the repeating unit (by) is hydrophobic, but is particularly preferable from the viewpoint of reducing development defects.

  As the repeating unit (by), for example, a repeating unit represented by the formula (K0) can be given.

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.

R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.

However, at least one of R _k1 and R _k2 represents a group containing a polarity converting group.

  The polarity converting group represents a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer as described above. The polar conversion group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.

Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.

The repeating unit (by) has a group that increases the solubility in a preferable alkali developer by having a group having a partial structure represented by the general formula (KA-1) or (KB-1). Is a bond having a bond as in the case of the partial structure represented by the general formula (KA-1) and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent. When it does not have, the group having a partial structure is a group having a monovalent or higher valent group excluding at least one arbitrary hydrogen atom in the partial structure.

  The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the resin (XA1) through a substituent at an arbitrary position.

  The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure (for example, an alicyclic structure) together with a group as X.

  X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a carbonic acid ester group. More preferably, it is a carboxylic acid ester group.

The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .

Z _ka1 represents a halogen atom, an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group. If Z _ka1 there are a plurality, each _{Z ka1} may or may not be the same.

Z _ka1 may be linked to form a ring. Examples of the ring formed by connecting Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).

  nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

The electron withdrawing group as Z _{ka1 is the same} as the electron withdrawing group as Y ¹ and Y ² described later. The electron withdrawing group may be substituted with another electron withdrawing group.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. The ether group is preferably an ether group substituted with an alkyl group or a cycloalkyl group, that is, an alkyl ether group. The electron withdrawing group is as defined above.

Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group as Z _ka1 may have a substituent and may be linear or branched. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. The branched alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms. C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, are preferable.

The cycloalkyl group as Z _ka1 may have a substituent, may be monocyclic,
It may be polycyclic. In the case of a polycyclic type, the cycloalkyl group may be a bridged type. That is, in this case, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group. As the cycloalkyl group, structural formulas (1) to (50) disclosed in paragraph 0619 of US Patent Publication No. 2012/0135348 are also preferable. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

  Preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group. And cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.

  Examples of the substituent of these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.

  Moreover, the said group may have a substituent further.

  X in the general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by the general formula (KA-1) is preferably a lactone ring, and more preferably a 5- to 7-membered lactone ring.

  In addition, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the structure.

  As for the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.

  As a structure containing a lactone ring structure represented by the general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. The lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14) and (KA-1-17).

The structure containing the lactone ring structure may or may not have a substituent. Preferable substituents include those similar to the substituent Z _ka1 that the ring structure represented by the general formula (KA-1) may have.

  Preferred examples of X in the general formula (KB-1) include a carboxylic acid ester group (—COO—).

Y ¹ and Y ² in formula (KB-1) each independently represent an electron-withdrawing group.

  The electron withdrawing group is a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond directly connected to (KA-1) or a bond directly connected to X in (KB-1).

In formula (EW),
R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

n _ew is the repeating number of the linking group represented by —C (R _ew1 ) (R _ew2 ) — and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.

Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo (cyclo) alkyl group or a haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , an oxy group, a carbonyl group, a sulfonyl group Examples thereof include a group, a sulfinyl group, and a combination thereof. The electron-withdrawing group may have the following structure, for example. The “halo (cyclo) alkyl group” represents an alkyl group and a cycloalkyl group that are at least partially halogenated, and the “haloaryl group” represents an aryl group that is at least partially halogenated. In the following structural formula, R _ew3 and R _ew4 each independently represent an arbitrary structure. R _ew3 and R _ew4 may have any structure, and the partial structure represented by the formula (EW) may have an electron withdrawing property, and may be linked to, for example, the main chain of the resin. An alkyl group and a fluorinated alkyl group;

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with an arbitrary atom or substituent. At least one group of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the resin (XA1) through a further substituent.

Y _ew1 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 .

At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group. Represents a fluoromethyl group.

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.

R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.

Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.

Examples of the (per) halocycloalkyl group and the (per) haloaryl group in R _{f1 to} R _f3 or in the ring formed by linking R _f2 and R _f3 include, for example, the aforementioned cycloalkyl group in Z _ka1 is a halogen atom. And a perfluoroaryl group represented by -C _(n) F _(n-1) and more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H Can be mentioned. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

The ring that may be formed by linking at least two of R _ew1 , R _ew2 and Y _ew1 preferably includes a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).

  In the repeating unit (by), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a general formula (KA) It may have both a partial structure represented by -1) and a partial structure represented by the general formula (KB-1).

Note that part or all of the partial structure of the general formula (KA-1) may also serve as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group functions as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). There is also a possibility.

  In addition, when the repeating unit (by) corresponds to the repeating unit (b *) or the repeating unit (b ″) and has a partial structure represented by the general formula (KA-1), the general formula (KA) As for the partial structure represented by -1), it is more preferable that the polarity conversion group is a partial structure represented by -COO- in the structure represented by the general formula (KA-1).

  The repeating unit (by) can be a repeating unit having a partial structure represented by the general formula (KY-0).

In the general formula (KY-0),
R ₂ represents a chain or cyclic alkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.

R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.

R ₄ is a halogen atom, cyano group, hydroxy group, amide group, alkyl group, cycloalkyl group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). When there are a plurality of R _{4 s} , they may be the same or different, and two or more R ₄ may be bonded to form a ring.

  X represents an alkylene group, an oxygen atom, or a sulfur atom.

  Z and Za represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of them, they may be the same or different.

  * Represents a bond to the main chain or side chain of the resin.

  o is the number of substituents and represents an integer of 1 to 7.

  m is the number of substituents and represents an integer of 0 to 7.

  n represents the number of repetitions and represents an integer of 0 to 5.

The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).

The preferred carbon number range and specific examples of the chain or cyclic alkylene group as R ₂ are the same as those described for the chain alkylene group and cyclic alkylene group in Z ₂ of the general formula (bb).

The linear, branched or cyclic hydrocarbon group as R ₃ has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and preferably 3 carbon atoms when branched. -30, more preferably 3-20, and in the case of a ring, it is 6-20. Specific examples of R ₃ include specific examples of the alkyl group and cycloalkyl group as Z _ka1 described above.

Preferred carbon numbers and specific examples of the alkyl group and cycloalkyl group as R ₄ and R are the same as those described in the alkyl group and cycloalkyl group as Z _ka1 described above.

The acyl group as R ₄ is preferably one having 1 to 6 carbon atoms, and examples thereof include a formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl group.

Examples of the alkyl moiety in the alkoxy group and alkoxycarbonyl group as R ₄ include a linear, branched or cyclic alkyl moiety, and the preferred carbon number of the alkyl moiety and specific examples thereof are those described above for Z _ka1. The same as those described in the alkyl group and cycloalkyl group.

Examples of the alkylene group as X include a chain or cyclic alkylene group, and preferred carbon numbers and specific examples thereof are the same as those described for the chain alkylene group and cyclic alkylene group as R ₂ .

  Moreover, the repeating unit which has a partial structure shown below as a specific structure of a repeating unit (by) is mentioned.

In general formulas (rf-1) and (rf-2),
X ′ represents an electron-attracting substituent, preferably a carbonyloxy group, an oxycarbonyl group, an alkylene group substituted with a fluorine atom, or a cycloalkylene group substituted with a fluorine atom.

  A represents a single bond or a divalent linking group represented by -C (Rx) (Ry)-. Here, Rx and Ry are each independently a hydrogen atom, a fluorine atom, an alkyl group (preferably having 1 to 6 carbon atoms and optionally substituted with a fluorine atom or the like), or a cycloalkyl group (preferably a carbon atom). And may be substituted with a fluorine atom or the like. Rx and Ry are preferably a hydrogen atom, an alkyl group, or an alkyl group substituted with a fluorine atom.

X represents an electron withdrawing group, and specific examples thereof include the above-mentioned electron withdrawing groups as Y ¹ and Y ² , preferably a fluorinated alkyl group or a fluorinated cycloalkyl group. An aryl group substituted with a fluorine or fluorinated alkyl group, an aralkyl group substituted with a fluorine or fluorinated alkyl group, a cyano group, or a nitro group.

  * Represents a bond to the main chain or side chain of the resin. That is, it represents a bond that bonds to the main chain of the resin through a single bond or a linking group.

  In addition, when X 'is a carbonyloxy group or an oxycarbonyl group, A is not a single bond.

  The polarity-converting group is decomposed by the action of an alkali developer and subjected to polarity conversion, whereby the solubility in an alkali solution can be improved.

  The repeating unit (by) is more preferably a repeating unit having at least two or more polar conversion groups.

  When the repeating unit (by) has at least two polar conversion groups, the repeating unit (by) preferably has a group having a partial structure having two polar conversion groups represented by the following general formula (KY-1). In addition, when the structure represented by general formula (KY-1) does not have a bond, it is a group having a monovalent or higher valent group in which at least one arbitrary hydrogen atom in this structure is removed.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (═O). May be formed.

R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the above formula (KB-1), and preferably a halogen atom or the above —C (R _f1 ) (R _f2 ) —R _f3. A halo (cyclo) alkyl group or a haloaryl group represented by the formula: Preferably _{R ky3} halogen atom, or, the _{-C (R f1)} (R f2) halo (cyclo) alkyl groups or haloaryl groups represented by _{-R f3,} lactone _{R ky2} is linked to _{R ky1} An electron withdrawing group that forms a ring or has no halogen atom.

R _ky1 , R _ky2 , and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.

Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in formula (KA-1).

As the lactone ring formed by linking R _ky1 and R _ky2 , the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the above formula (KB-1).

  The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.

Two or more of R _{ky6 to} R _ky10 may be linked to each other to form a monocyclic or polycyclic structure.

R _ky5 represents an electron withdrawing group. Examples of the electron withdrawing group include the same groups as those described above for Y ₁ and Y ₂ , preferably a halogen atom or a halo (cyclo (cyclo) represented by —C (R _f1 ) (R _f2 ) —R _f3 above. ) An alkyl group or a haloaryl group.

Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka1 in formula (KA-1).

  The structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

In the formula (KY-3), Z _ka1 and nka are each synonymous with the general formula (KA-1). R _ky5 is synonymous with the above formula (KY-2).

L _ky represents an alkylene group, an oxygen atom or a sulfur atom. _Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

  The repeating unit (b) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is. Examples include acrylate-based repeating units (including those having substituents at the α-position and β-position), styrene-based repeating units (including those having substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units Preferred are acrylate repeat units, vinyl ether repeat units, and norbornene repeat units, with acrylate repeat units being most preferred.

When the repeating unit (by) is a repeating unit having at least one of a fluorine atom, a silicon atom, and a CH ₃ partial structure (that is, when the repeating unit corresponds to the above repeating unit (b ′) or (b ″)), the repeating unit Examples of the partial structure having a fluorine atom in the unit (by) include the same as those mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably the general formula (F2) to In this case, the partial structure having a silicon atom in the repeating unit (by) is the same as that in the repeating unit having at least one of the fluorine atom and the silicon atom. And the same groups as those described above, preferably the groups represented by the above general formulas (CS-1) to (CS-3) It is possible.

  The content of the repeating unit (by) in the resin (XA1) is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, most preferably 50 to the total repeating units in the resin (XA1). 100 mol%.

  Specific examples of the repeating unit (by) having a group that increases the solubility in an alkali developer include the repeating unit disclosed in paragraph 0725 of US Patent Publication No. 2012/0135348. It is not limited.

  Examples of the method for synthesizing the monomer corresponding to the repeating unit (by) having the polar conversion group (y) as described above include the method described in International Publication No. 2010/069705, International Publication No. 2010/069705, or the like. Can be synthesized with reference to

  In the resin (XA1), the repeating unit (bz) having a group (z) that is decomposed by the action of an acid is an acid mentioned in the resin A contained in the actinic ray-sensitive or radiation-sensitive resin composition described later. Examples thereof include the same repeating units having a decomposable group.

  When the repeating unit (bz) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit corresponds to the above repeating unit (b ′) or (b ″)), the repeating unit (bz) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the above general formulas (CS-1) to (CS-3) can be exemplified.

  In the resin (XA1), the content of the repeating unit (bz) having a group (z) that decomposes by the action of an acid is preferably 10 to 100 mol% with respect to all the repeating units in the resin (XA1). Preferably it is 30-100 mol%, More preferably, it is 50-100 mol%.

  Hereinabove, the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has been described. The content of the repeating unit (b) in the resin (XA1) is as follows: 10-100 mol% is preferable with respect to all the repeating units in resin (XA1), More preferably, it is 30-100 mol%, Most preferably, it is 50-100 mol%.

  The content of the repeating unit (b ′) is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, and most preferably 50 to 100 mol% with respect to all the repeating units in the resin (XA1).

  The content of the repeating unit (b *) is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, still more preferably 5 to 70 mol%, most preferably 10 with respect to all repeating units in the resin (XA1). ~ 60 mol%. The content of the repeating unit having at least one of a fluorine atom and a silicon atom used together with the repeating unit (b *) is preferably 10 to 99 mol% with respect to all the repeating units in the resin (XA1), more preferably It is 20-97 mol%, More preferably, it is 30-95 mol%, Most preferably, it is 40-90 mol%.

  The content of the repeating unit (b ″) is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, and most preferably 50 to 100 mol% with respect to all the repeating units in the resin (XA1).

  The resin (XA1) may further have a repeating unit represented by the following general formula (CIII).

In general formula (CIII):
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 fluorine atom, a group containing a silicon atom, or the like.

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

In general formula (CIII), 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 a phenyl group or naphthyl group having 6 to 20 carbon atoms, 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 oxy group, a phenylene group, or an ester bond (a group represented by —COO—).

Specific examples of the repeating unit represented by the general formula (CIII) are listed below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN. Note that the repeating unit in the case where Ra is CF ₃ also corresponds to the repeating unit having at least one of the fluorine atom and the silicon atom.

  As for resin (XA1), it is natural that there are few impurities, such as a metal, It is preferable that a residual monomer and an oligomer component are 0-10 mass%, More preferably, 0-5 mass%, 0-1 Mass% is even more preferred. Thereby, the composition for pattern reversal without the foreign material in a liquid is obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably 1 to 1, in view of the shape of the pattern after inversion, roughness, and the like. .8, most preferably in the range of 1 to 1.5.

  As the resin (XA1), various commercially available products can be used, and the resin (XA1) 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 those described for the resin A described later.

  Specific examples of the resin (XA1) are shown below.

  The weight average molecular weight of the resin (XA1) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 35,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).

  The blending ratio of the resin (XA1) in the resin (XA) in the resin composition for pattern reversal is preferably 0.01 to 50 parts by mass, and 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (XA) component. Is more preferable, and 0.5 to 10 parts by mass is even more preferable.

[Resin (XA2)]
Resin (XA2) is preferably an alkali-insoluble resin when the treatment liquid of the present invention is an alkaline solution from the viewpoint of the persistence of the reverse pattern which is the second pattern.

  Here, the alkali-insoluble resin means a resin having a dissolution rate in an alkaline solution as defined above of less than 1 nm / sec. The dissolution rate of the alkali-insoluble resin (AX2) in the alkaline solution is preferably less than 0.1 nm / sec, more preferably less than 0.01 nm / sec, and even more preferably not dissolved.

  When an alkaline solution is used as the treatment liquid of the present invention, the resin (XA2) does not contain or contains an alkali-soluble group selected from the group consisting of the above (x) to (z) from the viewpoint of pattern persistence. In some cases, it is preferable that the dissolution rate of the resin (XA2) in the alkaline solution is within the above range.

  In one embodiment of the present invention, the resin (XA2) has a content of repeating units having an alkali-soluble group selected from the group consisting of the above (x) to (z) with respect to all the repeating units in the resin (XA2). 0 to 30 mol% is preferable, 0 to 10 mol% is more preferable, and 0 to 1 mol% is still more preferable.

The resin (XA2) is preferably one in which the resin (XA1) is unevenly distributed in the surface layer portion of the pattern reversal film that is the second film. From the viewpoint of uneven distribution, the resin (XA2) does not contain “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” (CH ₃ partial structure). If it is contained, it is preferably within the range shown below.

  That is, from the viewpoint of uneven distribution, the resin (XA2) preferably has a fluorine atom content of 0 to 20% by mass and 0 to 5% by mass with respect to the weight average molecular weight of the resin (XA2). It is more preferable. Moreover, it is preferable that it is 0-30 mol%, and, as for resin (XA2), the repeating unit containing a fluorine atom is 0-30 mol% with respect to all the repeating units in resin (XA2), and it is more preferable that it is 0-10 mol%. .

  Moreover, it is preferable that the content rate of a silicon atom is 0-30 mass% with respect to the weight average molecular weight of resin (XA2), and resin (XA2) is 0-20 mass% from a ubiquitous viewpoint. It is more preferable. Moreover, it is preferable that it is 0-30 mol%, and, as for resin (XA2), the repeating unit containing a silicon atom is 0-30 mol% with respect to all the repeating units in resin (XA2), and it is more preferable that it is 0-10 mol%. .

In addition, from the viewpoint of uneven distribution, the resin (XA2) preferably has 0 to 80 mol% of repeating units having a CH ₃ partial structure based on all repeating units in the resin (XA2). More preferably, it is mol%.

When both the resin (XA1) and the resin (XA2) have one or more of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin”, The surface energy of each resin is preferably in the relationship of resin (XA1) <resin (XA1). The surface energy according to the present invention can be calculated by measuring the contact angle using two or more kinds of liquids with known surface tensions.

  The resin (XA2) preferably has a group containing a ring structure, and more preferably contains a repeating unit containing a ring structure, from the viewpoint of etching resistance of the inverted pattern. The ring structure may be an alicyclic group or an aromatic group.

  The alicyclic group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane is preferable. Monocycloalkanes preferably have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, polycycloalkanes include polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like; condensed ring systems such as a cyclic group having a steroid skeleton A polycycloalkane having a polycyclic skeleton is more preferred.

  In the present specification, the “steroid skeleton” means a skeleton (st) represented by the following chemical formula in which three six-membered rings and one five-membered ring are connected.

  The repeating unit containing an alicyclic group is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, based on all repeating units in the resin (XA2).

  Specifically, the aromatic group is a group obtained by removing one hydrogen atom from an aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and one of the aromatic ring hydrogen atoms is substituted with an alkylene group. Groups (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.) and the like, It may have a substituent.

  The repeating unit containing an aromatic group is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, based on all repeating units in the resin (XA2).

  The resin (XA2) preferably has a group containing a silicon atom, and more preferably contains a repeating unit containing a silicon atom, from the viewpoint of etching resistance of the reverse pattern.

  The group containing a silicon atom preferably has an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.

  Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the general formulas (CS-1) to (CS-3) described in the resin (XA1).

  When the resin (XA2) contains a silicon atom from the viewpoint of etching resistance of the reverse pattern, the content of the silicon atom is preferably 1 to 30% by mass with respect to the weight average molecular weight of the resin (XA2). It is more preferable that it is 1-20 mass%. Moreover, it is preferable that it is 1-30 mol% with respect to all the repeating units in resin (XA2), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 1-10 mol%.

  As with the resin (XA1) described above, the resin (XA2) preferably has 0 to 10% by mass of residual monomer and oligomer components, and more preferably has few impurities such as metals. 0-5 mass% and 0-1 mass% are still more preferable. Thereby, a resin composition for pattern reversal free from foreign matter in the liquid is obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably 1 to 1 in terms of the pattern shape after inversion and roughness. 8, most preferably in the range of 1 to 1.5.

  As the resin (XA2), various commercially available products can be used, and as with the resin (XA1), it can be synthesized according to a conventional method.

  Specific examples of the resin (XA2) are shown below.

  The weight average molecular weight of the resin (XA2) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 35,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).

  The mixing ratio of the resin (XA2) in the resin (XA) in the resin composition for pattern reversal is preferably 30 to 99.5 parts by mass, more preferably 50 to 99 parts by mass with respect to 100 parts by mass of the resin (XA) component. 80 to 99 parts by mass are more preferable.

  Resin (XA2) can be used individually by 1 type or in combination of 2 or more types.

  The content of the resin component (XA) in the resin composition for pattern reversal is usually 30 to 100% by mass based on the total solid content (components other than the solvent described later) in the resin composition for pattern reversal, Preferably it is 50-100 mass%, More preferably, it is 80-100 mass%.

<Heat acid generator>
The resin composition for pattern inversion may further contain a thermal acid generator.
Although it does not specifically limit as a thermal acid generator, For example, isopropyl-p-toluenesulfonate, cyclohexyl-p-toluenesulfonate, Sanshin Chemical Industries sun aid SI series and San Apro CPI series which are aromatic sulfonium salt compounds, etc. Is mentioned. When the thermal acid generator is added, the pattern reversal film is formed and then baked, whereby the polarity of the resin (A) is further increased by the action of the acid and the alkali solubility can be improved.

  As a content rate of a thermal acid generator, it is 0.1-10 mass% normally with respect to the total solid in the resin composition for pattern inversion, Preferably it is 1-5 mass%.

<Surfactant>
An appropriate amount of a surfactant can be added to the pattern reversal resin composition of the present invention, if necessary.

  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.

  As content rate of surfactant, it is 0.001-5 mass% normally with respect to the total solid in the resin composition for pattern inversion, Preferably it is 0.005-2 mass%, More preferably, it is 0.01-0. 0.5% by mass.

<Other additives>
The resin composition for pattern reversal of the present invention may contain additives other than the above-mentioned thermal acid generator and interface generator as additives, such as a photoacid generator, a photobase generator, It may contain a thermal base generator.

<Organic solvent>
The resin composition for pattern reversal of the present invention preferably contains an organic solvent (XS).
The organic solvent (XS) may be any organic solvent that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition described below, as long as it can dissolve the components blended in the pattern reversal resin composition. The organic solvent used for the developing solution containing a solvent and the solvent illustrated to the organic solvent used for the rinse liquid mentioned above can be used.

  The organic solvent (XS) is preferably an organic solvent that does not dissolve the first resist pattern. “Do not dissolve the first resist pattern” in the organic solvent (XS) means that an actinic ray-sensitive or radiation-sensitive resin composition is applied on a support and dried, and the film thickness is 0 at 23 ° C. When an actinic ray-sensitive or radiation-sensitive film having a thickness of 2 μm is formed and immersed in an organic solvent (XS), the loss or thickness of the actinic ray-sensitive or radiation-sensitive film is lost even after 60 minutes. (Notably, the actinic ray-sensitive or radiation-sensitive film does not have a thickness of 0.16 μm or less).

  An organic solvent (XS) can be used individually by 1 type or in combination of 2 or more types.

  1.0-10.0 mass% is preferable and, as for the solid content concentration in the resin composition for pattern inversion of this invention, 1.0-6.0 mass% is more preferable.

<< Actinic ray-sensitive or radiation-sensitive resin composition >>
The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention may be used for negative development, i.e., development in which an exposed portion remains as a pattern and an unexposed portion is removed. Alternatively, it may be used for positive development, that is, development in which an exposed portion is removed and an unexposed portion remains as a pattern.

  The actinic ray-sensitive or radiation-sensitive resin composition is typically a resist composition, since a particularly high effect can be obtained. The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention is typically a chemically amplified resist composition.

  The components contained in the actinic ray-sensitive or radiation-sensitive resin composition will be described below.

<Resin (A)>
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin (A) whose polarity is increased by the action of an acid. Resin (A) is a resin whose polarity is increased by the action of an acid and its solubility in an organic developer decreases when negative development using a developer containing an organic solvent is performed, In the case of performing positive development using an alkali developer, it is a resin whose polarity is increased by the action of an acid and its solubility in an alkali developer is increased.

[Repeating unit having acid-decomposable group (a)]
Resin (A) includes a repeating unit (a) having a group that is decomposed by the action of an acid to generate a polar group (hereinafter also referred to as “acid-decomposable group”) as a group that increases in polarity by the action of an acid. It is preferable to include. The repeating unit (a) having an acid-decomposable group is, for example, a repeating unit having an acid-decomposable group in the main chain or side chain of the resin, or in both the main chain and side chain. The group generated by the decomposition of the acid-decomposable group is preferably a polar group because, for example, the affinity with a developer containing an organic solvent is lowered, and insolubilization or insolubilization (negative conversion) proceeds. The polar group is more preferably an acidic group. The definition of the polar group is synonymous with the definition described in the section of the repeating unit (b) described later. Examples of the polar group generated by the decomposition of the acid-decomposable group include an alcoholic hydroxyl group, an amino group, and an acidic group. Is mentioned.

  The polar group generated by the decomposition of the acid-decomposable group is preferably an acidic group.

  The acidic group is not particularly limited as long as it is a group that is insolubilized in a developer containing an organic solvent, but is preferably a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, a fluorinated alcohol group, or a sulfonamide group. 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 (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, more preferably carboxylic acid group, fluorinated alcohol group (preferably hexafluoroisopropanol), phenol Hydroxyl group, (used as a developer for conventional resist, a group dissociated in 2.38 mass% tetramethylammonium hydroxide aqueous solution) acidic group such as a sulfonic acid group include.

  Preferred groups as the acid-decomposable group are groups in which the hydrogen atom of these groups is substituted with a group capable of leaving by the action of an acid.

  As the acid-decomposable group, a group that decomposes by the action of an acid to generate an alcoholic hydroxyl group is also preferable.

Examples of the group capable of leaving by the action of an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and -C (R _{01) (R} 02) _(can be exemplified _{OR 39)} or the like.

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group.

  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.

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

In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 19 carbon atoms. Z represents a substituent. p represents 0 or a positive integer, preferably 0 to 2, and more preferably 0 or 1. When a plurality of Z are present, they may be the same as or different from each other. Z is preferably a group consisting of only a hydrogen atom and a carbon atom from the viewpoint of increasing the dissolution contrast with respect to a developer containing an organic solvent before and after acid decomposition, for example, a linear or branched alkyl group, A cycloalkyl group is preferred.

  The resin (A) may contain a repeating unit represented by the following general formula (VI) as the repeating unit (a).

In general formula (VI),
R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, and R ₆₂ in this case represents a single bond or an alkylene group.

X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.

L ₆ represents a single bond or an alkylene group.

Ar ₆ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R ₆₂ to form a ring.

Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group capable of leaving by the action of an acid.

  n represents an integer of 1 to 4.

  As a detailed description and specific examples of the repeating unit represented by the general formula (VI), the descriptions in paragraphs 0040 to 0058 of JP-A-2014-106298 can be used, and the contents thereof are described in the present specification. Incorporated.

  One type of repeating unit having the acid-decomposable group may be used, or two or more types may be used in combination.

  The content of the repeating unit having an acid-decomposable group in the resin (A) (the total when containing plural types of repeating units having an acid-decomposable group) is 5 with respect to all repeating units in the resin (A). It is preferably from mol% to 80 mol%, more preferably from 5 mol% to 75 mol%, still more preferably from 10 mol% to 65 mol%.

[Repeating unit having polar group (b)]
The resin (A) preferably contains a repeating unit (b) having a polar group. By including the repeating unit (b), for example, the sensitivity of the composition containing a resin can be improved. The repeating unit (b) is preferably a non-acid-decomposable repeating unit (that is, having no acid-decomposable group).

  Examples of the “polar group” that the repeating unit (b) may contain include the following (1) to (4). In the following, “electronegativity” means a value by Pauling.

(1) A functional group including a structure in which an oxygen atom and an atom having an electronegativity difference of 1.1 or more are bonded by a single bond. Examples of such a polar group include a hydroxy group and the like. And a group containing a structure represented by O—H.

(2) Functional group including a structure in which a nitrogen atom and an atom having a difference in electronegativity of the nitrogen atom of 0.6 or more are bonded by a single bond. Examples of such a polar group include an amino group and the like. And a group containing a structure represented by N—H.

(3) Functional group including a structure in which two atoms having electronegativity different by 0.5 or more are bonded by a double bond or a triple bond. Examples of such a polar group include C≡N, C═O, N = And a group containing a structure represented by O, S═O or C═N.

(4) Functional group having an ionic moiety Examples of such a polar group include a group having a moiety represented by N ⁺ or S ⁺ .

  The repeating unit (b) may be a repeating unit having a lactone structure as a polar group.

  The repeating unit having a lactone structure is more preferably a repeating unit represented by the following general formula (AII).

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).

Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these. Ab is preferably a single bond or a divalent linking group represented by —Ab ₁ —CO ₂ —.

Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

  V represents a group having a lactone structure.

  As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), and (LC1-14).

The lactone 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 monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 2 to 8 carbon atoms. , 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. and n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

  The repeating unit having a lactone group 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 resin (A) may or may not contain a repeating unit having a lactone structure, but when it contains a repeating unit having a lactone structure, the content of the repeating unit in the resin (A) is The range of 1 to 70 mol% is preferable with respect to the repeating unit, more preferably 3 to 65 mol%, and still more preferably 5 to 60 mol%.

  As specific examples of the repeating unit having a lactone structure in the resin (A), specific examples described in paragraphs 0094 to 0095 of JP-A-2014-106298 can be used, and the contents thereof are described in this specification. Incorporated.

  Moreover, it is also one of the especially preferable aspects that the polar group which a repeating unit (b) can have is an acidic group. Preferable acidic groups include phenolic hydroxyl group, carboxylic acid group, sulfonic acid group, fluorinated alcohol group (for example, hexafluoroisopropanol group), sulfonamide group, 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 (alkylcarbonyl) methylene group, A tris (alkylsulfonyl) methylene group is mentioned. Of these, the repeating unit (b) is more preferably a repeating unit having a carboxyl group. By containing the repeating unit having an acidic group, the resolution in the contact hole application is increased. The repeating unit having an acidic group includes a repeating unit in which an acidic group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acidic group in the main chain of the resin through a linking group. It is preferable to use a polymerization initiator or a chain transfer agent having a repeating unit bonded to each other, or an acidic group, at the time of polymerization and introduce it at the end of the polymer chain. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  The acidic group that the repeating unit (b) can have may or may not contain an aromatic ring, but when it has an aromatic ring, it is preferably selected from acidic groups other than phenolic hydroxyl groups. When the repeating unit (b) has an acidic group, the content of the repeating unit having an acidic group is preferably 30 mol% or less, preferably 20 mol% or less, based on all repeating units in the resin (A). More preferably. When resin (A) contains the repeating unit which has an acidic group, content of the repeating unit which has an acidic group in resin (A) is 1 mol% or more normally.

  As specific examples of the repeating unit having an acidic group, specific examples described in paragraph 0098 of JP-A-2014-106298 can be used, and the contents thereof are incorporated in the present specification.

  Moreover, resin (A) may contain the repeating unit which has the group which generate | occur | produces an acid by irradiation of actinic light or a radiation.

Examples of the repeating unit having a group capable of generating an acid upon irradiation with actinic rays or radiation include, for example, a repeating unit having an onium cation contained in each of resins P-65 to P-70 of specific examples of the resin (A) described later. Examples include units.
[Repeating unit having aromatic ring group (c)]
In a preferred embodiment, the resin (A) may have a repeating unit (c) having an aromatic ring group.

  Preferred examples of the repeating unit (c) having an aromatic ring group include a repeating unit having a phenolic hydroxyl group.

  In this specification, the phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxy group. The aromatic ring of the aromatic ring group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

  In particular, when electron beam or extreme ultraviolet exposure is used as the exposure light source in the exposure step (b), the resin (A) preferably has a repeating unit having a phenolic hydroxyl group.

  As a repeating unit which has a phenolic hydroxyl group, the repeating unit represented by the following general formula (I) or (I-1) is mentioned, for example.

Where
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may form a ring with Ar _4, R ₄₂ in this case represents a single bond or an alkylene group.

X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.

L ₄ each independently represents a single bond or a divalent linking group.

Ar ₄ represents an (n + 1) -valent aromatic ring group, and when bonded to R ₄₂ to form a ring, represents an (n + 2) -valent aromatic ring group.

  n represents an integer of 1 to 5.

For the purpose of making the repeating unit of the general formula (I) or (I-1) highly polar, it is also preferable that n is an integer of 2 or more, or X ₄ is —COO— or —CONR ₆₄ —.

As the alkyl group of R ₄₁ , R ₄₂ and R _{43 in} the general formulas (I) and (I-1), a methyl group, an ethyl group, a propyl group, an isopropyl group, n which may have a substituent is preferable. -Alkyl groups having 20 or less carbon atoms such as butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group are mentioned, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably carbon number. Examples of the alkyl group are 3 or less.

The cycloalkyl group of R ₄₁ , R ₄₂ and R _{43 in} the general formulas (I) and (I-1) may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.

Examples of the halogen atom of R ₄₁ , R ₄₂ , and R _{43 in} the general formulas (I) and (I-1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.

As the alkyl group contained in the alkoxycarbonyl group of R ₄₁ , R ₄₂ , and R _{43 in} the general formulas (I) and (I-1), the same alkyl groups as those in the above R ₄₁ , R ₄₂ , and R ₄₃ are preferable. .

  Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the substituent preferably has 8 or less carbon atoms.

Ar ₄ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, or Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

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

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

Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n + 1) -valent aromatic ring group may have include alkyls exemplified as R ₄₁ , R ₄₂ , and R ₄₃ in formula (I). Group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group and other alkoxy groups; phenyl group and other aryl groups; and the like.

_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64} in, preferably an optionally substituted methyl group, an ethyl group, a propyl group , An isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group, or the like, and an alkyl group having a carbon number of 8 or less is more preferable. Can be mentioned.

X ₄ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

The divalent linking group as L ₄ is preferably an alkylene group, and the alkylene group is preferably an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group. And those having 1 to 8 carbon atoms such as an octylene group.

As Ar ₄ , an aromatic ring group having 6 to 18 carbon atoms which may have a substituent is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.

The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar ₄ is preferably a benzene ring group.

  The repeating unit having a phenolic hydroxyl group contained in the resin (A) is preferably a repeating unit represented by the following general formula (p1).

  R in the general formula (p1) represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. As R in the general formula (p1), a hydrogen atom is particularly preferable.

  Ar in the general formula (p1) represents an aromatic ring, for example, an aromatic carbon which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, or the like. A hydrogen ring or a heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc. And aromatic ring heterocycles. Of these, a benzene ring is most preferable.

  M in the general formula (p1) represents an integer of 1 to 5, and is preferably 1.

  Hereinafter, although the specific example of the repeating unit which has the phenolic hydroxyl group which resin (A) has is shown, this invention is not limited to this. In the formula, a represents 1 or 2.

  Resin (A) may have 1 type of repeating units which have a phenolic hydroxyl group, or may have 2 or more types.

  The content of the repeating unit having a phenolic hydroxyl group is preferably from 10 to 95 mol%, more preferably from 20 to 90 mol%, more preferably from 30 to 85, based on all repeating units of the resin (A). More preferably, it is mol%.

  Further, the repeating unit (c) having an aromatic ring group may have an aromatic ring group in the above-described repeating unit (a) having an acid-decomposable group or repeating unit (b) having a polar group. .

  Resin (A) may have 1 type of repeating units (c) which have an aromatic ring group, or may have 2 or more types.

  The content of the repeating unit (c) having an aromatic ring group is preferably 5 to 100 mol%, more preferably 7 to 98 mol%, based on all repeating units of the resin (A). More preferably, it is 8 to 96 mol%.

  In the resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition, the content molar ratio of each repeating structural unit is the resist standard developer compatibility, substrate adhesion, resist profile, and general resist characteristics. It is appropriately set in order to adjust the necessary performance such as resolving power, heat resistance, sensitivity, and the like.

  The molecular weight of the resin (A) is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 60000, and particularly in the range of 2000 to 30000. preferable. By setting the weight average molecular weight in the range of 1000 to 100,000, it is possible to prevent heat resistance and dry etching resistance from being deteriorated, and also to prevent developability from being deteriorated and the film forming property from being deteriorated due to increased viscosity. be able to. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (Gel Permeation Chromatography) (carrier: THF (Tetrahydrofuran) or N-methyl-2-pyrrolidone).

  The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

  Resin (A) can be used individually by 1 type or in combination of 2 or more types. The content of the resin (A) is preferably 20 to 99% by mass, more preferably 30 to 89% by mass, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. 40-79 mass% is especially preferable.

  As specific examples of the resin (A), specific examples described in paragraphs 0120 to 0125 of JP-A-2014-106298 can be used, and the contents thereof are incorporated herein.

<Compound that generates acid upon irradiation with actinic ray or radiation>
The actinic ray-sensitive or radiation-sensitive resin composition preferably contains a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”).

  The acid generator is not particularly limited as long as it is a publicly known acid generator, but upon irradiation with actinic rays or radiation, at least any of organic acids such as sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide. Compounds that generate such are preferred.

  More preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (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).

Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

  Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). 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, an alkyl group (preferably C1-C15) can further be mentioned 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.

  The alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.

Examples of other non-nucleophilic anions include fluorinated phosphorus (eg, PF ₆ ⁻ ), fluorinated boron (eg, BF ₄ ⁻ ), and fluorinated antimony (eg, SbF ₆ ⁻ ). .

  Examples of the non-nucleophilic anion include an aliphatic sulfonate anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.

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

  Moreover, as a non-nucleophilic anion, the anion represented with the following general formula (AN1) is also mentioned as a preferable aspect.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R ¹ and R ² , they may be the same or different.

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

  A represents a cyclic organic group.

  x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

  The general formula (AN1) will be described in more detail.

  The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. 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. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ may be mentioned, among which a fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _{15. , C 8 F 17, CH 2} CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which CF ₃ is preferable.

R ¹ and R ² are preferably a fluorine atom or CF ₃ .

  x is preferably 1 to 10, and more preferably 1 to 5.

  y is preferably 0 to 4, and more preferably 0.

  z is preferably 0 to 5, and more preferably 0 to 3.

The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred. Among these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

  The cyclic organic group 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 aromaticity but also aromaticity). And the like).

  The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. 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, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.

  Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

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

  In addition, examples of the cyclic organic group may include a lactone structure, and specific examples include those represented by the general formulas (LC1-1) to (LC1-17) that the resin (A) may have. Can be mentioned.

  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), cyclo Alkyl group (which may be monocyclic, polycyclic or spirocyclic, preferably 3 to 20 carbon atoms), aryl group (preferably 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 and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

_Examples of the organic group for R ₂₀₁ , R _202, and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.

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. Preferred examples of the alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. These groups 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.

  As specific examples of the acid generator, specific examples described in paragraphs 0162 to 0168 of JP-A-2014-106298 can be used, and the contents thereof are incorporated in the present specification.

  An acid generator can be used individually by 1 type or in combination of 2 or more types.

  Moreover, the content rate of a photo-acid generator becomes like this. Preferably it is 0.1-50 mass% on the basis of the total solid of actinic-ray-sensitive or radiation-sensitive resin composition, More preferably, it is 0.5-45. It is mass%, More preferably, it is 1-40 mass%.

<Solvent (coating solvent)>
The solvent that can be used in preparing the composition is not particularly limited as long as it dissolves each component. For example, alkylene glycol monoalkyl ether carboxylate (Propylene Glycol Monomethyl Ether Acetate: PGMEA) Alias 1-methoxy-2-acetoxypropane), alkylene glycol monoalkyl ether (propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol), etc.), lactate alkyl ester (ethyl lactate, Methyl lactate, etc.), cyclic lactone (γ-butyrolactone, etc., preferably 4-10 carbon atoms), chain or cyclic ketone (2-heptanone, cyclohexanone, etc., preferably 4-10 carbon atoms), al Examples include xylene carbonate (ethylene carbonate, propylene carbonate, etc.), alkyl carboxylates (preferably alkyl acetates such as butyl acetate), alkyl alkoxyacetates (ethyl ethoxypropionate), and the like. Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

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

  These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.

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

<Basic compound>
In the present invention, the actinic ray-sensitive or radiation-sensitive resin composition may further contain a basic compound. The basic compound is preferably a compound having a stronger basicity than phenol. Moreover, this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.

  Although the nitrogen-containing basic compound which can be used is not specifically limited, For example, the compound classified into the following (a)-(ki) can be used.

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

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

  Although carbon number of the alkyl group as R is not specifically limited, Usually, it is 1-20, Preferably it is 1-12.

  Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, it is 3-20, Preferably it is 5-15.

  Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.

  Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specific examples include a benzyl group.

  In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

  In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

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

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

(U) Ammonium salt As the basic compound, an ammonium salt can also be used as appropriate. Examples of the anion of the ammonium salt include halides, sulfonates, borates, and phosphates. Of these, halides and sulfonates are particularly preferred.

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

  The alkyl group contained in the alkyl sulfonate may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

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

  The ammonium salt may be hydroxide or carboxylate. In this case, the ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, or the like, or Particularly preferred are ammonium carboxylates such as the compound (Q-2) described later.

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

  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, and a carbamate group or a hemiaminal ether group. It is particularly preferred.

  The molecular weight of the low molecular weight compound (D) 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 (D), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

  Compound (D) 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),
R ′ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.
R ′ 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.
The specific structure of such a group is shown below.

  The compound (D) can also be constituted by arbitrarily combining the basic compound and the structure represented by the general formula (d-1).

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

  The compound (D) may correspond to the above basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

  In the general formula (A), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.

  Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. However, in -C (Rb) (Rb) (Rb), when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.

  At least two Rb may be bonded to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.

  n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

  In general formula (A), the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Ra and Rb are functional groups such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group and oxo group. , An alkoxy group and a halogen atom may be substituted. The same applies to the alkoxyalkyl group represented by Rb.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group of the Ra and / or Rb (these alkyl group, cycloalkyl group, aryl group, and aralkyl group are substituted with the functional group, alkoxy group, or halogen atom). As may be)
For example, a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., a group derived from these alkanes, for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, groups derived from these cycloalkanes, for example, methyl group, ethyl group, n-propyl group, a group substituted with one or more linear or branched alkyl groups such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like,
Groups derived from aromatic compounds such as benzene, naphthalene, anthracene, etc., and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 A group substituted with one or more linear or branched alkyl groups such as -methylpropyl group, 1-methylpropyl group, t-butyl group, and the like;
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, benzimidazole, and groups derived from these heterocyclic compounds are linear or branched A group substituted with one or more groups derived from an alkyl group or aromatic compound, a group derived from a linear or branched alkane, a group derived from a cycloalkane, a phenyl group, a naphthyl group A group substituted with one or more groups derived from an aromatic compound such as anthracenyl group or the like, or the above substituent is a hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo And a group substituted with a functional group such as a group.

  Examples of the divalent heterocyclic hydrocarbon group (preferably having a carbon number of 1 to 20) or a derivative thereof formed by bonding the Ra to each other include, 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 Groups derived from heterocyclic compounds such as indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, groups derived from these heterocyclic compounds A group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino And groups substituted with one or more functional groups such as a group, a morpholino group and an oxo group.

  As the particularly preferable compound (D) in the present invention, specific examples described in paragraphs 0258 to 0260 of JP-A-2014-106298 can be used, and the contents thereof are incorporated herein.

  The compound represented by the general formula (A) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.

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

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

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

  In addition to the above, the nitrogen-containing basic compound has a proton acceptor functional group and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease or disappearance of the proton acceptor, or an acid from the proton acceptor Examples thereof include compounds that generate a compound that has changed to guanidine, or guanidine compounds. For the detailed description and specific examples of these compounds, the description in paragraphs 0201 to 0236 of JP-A-2014-106298 can be incorporated, and the contents thereof are incorporated herein.

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

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

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

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

  When the composition according to the present invention contains a basic compound, the content is preferably 0.01 to 8.0% by mass based on the total solid content of the composition, More preferably, it is 5.0 mass%, and it is especially preferable that it is 0.2-4.0 mass%.

  The molar ratio of the basic compound to the photoacid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, More preferably, it is 0.1-3.

<Hydrophobic resin (HR)>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a hydrophobic resin (HR) separately from the resin (A).

  Since the hydrophobic resin (HR) is unevenly distributed on the film surface, the hydrophobic resin (HR) preferably contains a group having a fluorine atom, a group having a silicon atom, or a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Specific examples of the hydrophobic resin (HR) are shown below.

  As the hydrophobic resin, those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used. Hydrophobic resin can be used individually by 1 type or in combination of 2 or more types.

<Surfactant>
The actinic ray-sensitive or radiation-sensitive composition according to the present invention may further contain a surfactant. As this surfactant, fluorine-based and / or silicon-based surfactants are particularly preferable.

  Examples of the fluorine-based and / or silicon-based surfactant include Megafac F176 and Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656 and PF6320 manufactured by OMNOVA, and Troisol S manufactured by Troy Chemical Co., Ltd. -366, Fluorard FC430 manufactured by Sumitomo 3M Limited, and polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

  Surfactants other than fluorine and / or silicon may be used. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] and after in US 2008 / 0248425A1.

  One type of surfactant may be used alone, or two or more types may be used in combination.

  When the actinic ray-sensitive or radiation-sensitive resin composition further contains a surfactant, the amount used is preferably 0.0001 to 2% by mass based on the total solid content of the composition, and more Preferably it is 0.001-1 mass%.

<Other additives>
In addition to the components described above, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has a molecular weight of 3000 or less as described in carboxylic acid, carboxylic acid onium salt, Proceeding of SPIE, 2724, 355 (1996) and the like. In addition, a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, an antioxidant and the like can be appropriately contained.

  In particular, carboxylic acid is preferably used for improving the performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.

  The content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 3% by mass in the total solid content concentration of the composition.

  The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably used at a thickness of 10 to 250 nm, more preferably at a thickness of 20 to 200 nm, from the viewpoint of improving resolution. More preferably, it is preferably used at 30 to 100 nm. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.

  The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0. It is -5.3 mass%. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the substrate, and further, a resist pattern having excellent line width roughness can be formed. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.

  The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the above components are dissolved in a predetermined organic solvent, preferably the above mixed solvent, filtered, and then applied onto a predetermined support (substrate). Use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

  Various materials used in the pattern forming method of the present invention (for example, resin, solvent, developer, rinse solution, image reversal resin composition, actinic ray sensitive or radiation sensitive resin composition, antireflection film forming composition) Products, topcoat forming compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 10 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less.

  Examples of the method for removing impurities such as metals from the various materials described above include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.

  In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent metal impurities from being mixed in the manufacturing process. Whether or not the metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing apparatus. The content of the metal component contained in the cleaning liquid after use is more preferably 100 ppt (parts per trigger) or less, further preferably 10 ppt or less, and particularly preferably 1 ppt or less.

  In addition, as a method for reducing impurities such as metals contained in the various materials described above, a material having a low metal content is selected as a material constituting the various materials, and filter filtration is performed on the materials constituting the various materials. Examples of the method include distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark). The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.

  In addition, you may produce the mold for imprint using the inversion pattern formation method which concerns on this invention.

  A method for improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention. As a method for improving the surface roughness of the pattern, for example, a method of treating a resist pattern with a plasma of a hydrogen-containing gas disclosed in International Publication Pamphlet 2014/002808 can be mentioned. In addition, JP 2004-235468, US Published Patent Application 2010/0020297, JP 2009-19969, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.

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

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

  The present invention also relates to a method for manufacturing an electronic device including the above-described reverse pattern forming method of the present invention.

  The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Appliance) / media related equipment, optical equipment, communication equipment, etc.).

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not limited by this.
<< Preparation of Resin Composition for Pattern Reversal >>
[resin]
As resins used for the resin composition for pattern reversal, the following resins NP-1 to NP-12 and resins P-1 to P-7 were synthesized by a known method.

About each obtained resin, a GPC (Gel Permeation Chromatography) (carrier: tetrahydrofuran) measurement WHEREIN: A weight average molecular weight (Mw), a number average molecular weight (Mn: polystyrene conversion), and dispersion degree (Mw / Mn, hereafter "Pd") Was calculated. Further, the composition ratio (molar ratio) of the repeating units was calculated by ¹ H-NMR (Nuclear Magnetic Resonance) and ¹³ C-NMR measurement.

[Resin (XA2)]

[Dissolution rate in alkaline solution]
Each resin was dissolved in PGMEA to prepare a composition consisting only of a resin and a solvent.

  The above composition was applied onto a silicon wafer to form a 200 nm film made of only resin by a spin coating method. This film was immersed in a 2.38 mass% TMAH aqueous solution at 23 ° C., the film thickness after immersion was measured, and the dissolution rate was determined from the following formula.

Dissolution rate [nm / sec] = (film thickness before immersion [nm] −film thickness after immersion [nm]) / immersion time [second]
[Fluorine atom content]
Content R _F of the fluorine atoms in each resin _(mass%) by the following equation (1), after obtaining the content M _F of fluorine atoms in each monomer was determined by the following equation (2).

-Fluorine atom content M _F (% by mass) in each monomer
= [Molecular weight of fluorine atom in each monomer / molecular weight of monomer] × 100 Formula (1)
-Content of fluorine atom in resin R _F (mass%)
= Σ (molecular weight of each monomer x fluorine atom content in each monomer M _F x composition ratio of each monomer) / Σ (molecular weight of each monomer x composition ratio of each monomer) Equation (2)
[Content of silicon atom]
Content R _Si of the silicon atoms in each resin _(mass%) by the following equation (3), after obtaining the content M _Si of the silicon atom in each monomer was determined by the following equation (4).

-Content of silicon atom in each monomer M _Si (mass%)
= [Molecular weight of silicon atom in each monomer / molecular weight of monomer] × 100 formula (3)
-Content of silicon atoms in the resin R _Si (mass%)
= Σ (Molecular weight of each monomer × Silicon atom content M _{Si in} each monomer × Composition ratio of each monomer) / Σ (Molecular weight of each monomer × Composition ratio of each monomer) Equation (4)
<Preparation of resin composition for pattern reversal>
The components shown in Table 3 below are dissolved in the solvent shown in the same table to prepare a solution having a solid content concentration of 2.0% by mass, and this is filtered through a polyethylene filter having a pore size of 0.04 μm. Compositions (R-01) to (R-28) and (CR-1) to (CR-2) were prepared.

  The resins RP-1 and RP-2 contained in the compositions CR-1 and CR-2 are the same as the resins RP-1 and RP-2 used in the preparation of the resist composition described later.

  Abbreviations other than resin in Table 3 are as follows.

[Surfactant]
The following compounds were used as surfactants.

W-1: PF6320 (manufactured by OMNOVA; fluorine-based)
[Thermal acid generator]
The following compounds were used as thermal acid generators.

X-1: CPI-100P (manufactured by Sun Apro)
[solvent]
The following were used as solvents.

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-3: Butyl acetate << Preparation of actinic ray-sensitive or radiation-sensitive resin composition >>
[Acid-decomposable resin]
Resins RP1 to RP4 shown below were synthesized by known methods as acid-decomposable resins used for the actinic ray-sensitive or radiation-sensitive resin composition (resist composition).

About each obtained resin, a GPC (Gel Permeation Chromatography) (carrier: tetrahydrofuran) measurement WHEREIN: A weight average molecular weight (Mw), a number average molecular weight (Mn: polystyrene conversion), and dispersion degree (Mw / Mn, hereafter "Pd") Was calculated. Further, the composition ratio (molar ratio) of the repeating units was calculated by ¹ H-NMR (Nuclear Magnetic Resonance) and ¹³ C-NMR measurement.

<Preparation of resist composition>
The components shown in Tables 4 to 6 below are dissolved in the solvents shown in the respective tables, and solutions having the solid content concentrations shown in the respective tables are prepared, and this is filtered through a polyethylene filter having a pore size of 0.04 μm, and a resist is obtained. Compositions (Ar-01), (Ar-02), (EB-01) and (EUV-01) were prepared.

  Abbreviations other than the acid-decomposable resins in Tables 4 to 6 are as follows.

[Photoacid generator]
The following compounds were used as photoacid generators.

[Basic compounds]
The following compounds were used as basic compounds.

[Hydrophobic resin]
The following resins were used as hydrophobic resins. It shows with the composition ratio of each repeating unit, a weight average molecular weight (Mw), and dispersion degree (Pd). These were calculated | required by the method similar to the acid-decomposable resin mentioned above.

[solvent]
The following were used as solvents.

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
<Pattern formation>
[Resist film (first film) formation process]
First, a Brewer antireflection film ARC29A was applied on a silicon wafer by a spin coating method, and then baked at 205 ° C. for 60 seconds to form an underlayer (antireflection film) having a thickness of 86 nm.

  Next, the resist composition described in Tables 4 to 6 is applied on the formed underlayer (antireflection film), and then baked under the conditions described in the column “PB” in Table 7 below. PB), and a resist film was formed on the underlayer. Table 7 shows the thickness of the formed resist film.

[Exposure process]
(Exposure process-ArF immersion)
The resulting resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (XT1700i, NA1.20, Annular, outer sigma 0.95, inner sigma 0.7, manufactured by ASML). As the reticle, a reticle having a half pitch of 48 nm line and space of 1: 1 was used. The dimensions are based on the optical image at the time of projection. Moreover, ultrapure water was used as the immersion liquid.

  Thereafter, the substrate was baked under the conditions described in the column “PEB” in Table 7 (Post Exposure Bake; PEB), and then cooled to room temperature.

(Exposure process-EB)
Pattern irradiation was performed with respect to the obtained resist film using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). At this time, drawing was performed so that a line and space with a half pitch of 50 nm was formed.

  After the electron beam drawing, the resultant was baked (PEB) under the conditions described in the column “PEB” in Table 7, and then cooled to room temperature.

(Exposure process-EUV)
The obtained resist film was subjected to pattern exposure using an EUV exposure apparatus (Micro Exposure Tool, manufactured by Exitech, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). A mask having a half pitch of 30 nm line and space of 1: 1 was used as the mask.

  Then, after baking (PEB) on the conditions described in the column of “PEB” in Table 7, it was cooled to room temperature.

[Development process]
Next, development was performed.
Specifically, development was performed with the developer and development time shown in Table 7, and those described were rinsed with a rinse solution for 30 seconds. Thereafter, baking was performed under the conditions described in the column “Bake after development” in Table 7.

  Thus, a resist pattern having a line pattern and space pattern dimension of 1: 2 was obtained (see FIG. 2A).

[Pattern reversal film (second film) formation process]
To the obtained resist pattern, the resin composition for pattern reversal shown in Table 3 was applied and spin-coated so as to have the film thickness shown in Table 7. Then, in the column of “Bake after application” in Table 7 Baking was performed under the conditions described to form a pattern reversal film on the pattern.

[Pattern reversal process]
Next, peeling treatment using an alkaline solution was performed to obtain a reverse pattern.
Specifically, development was performed with the alkaline solution and development time shown in Table 7, and rinsed for 30 seconds. Then, it baked on the conditions as described in the column of "Bake after rinse".

  In this way, a resist pattern in which the dimensions of the line pattern and the space pattern were reversed to 2: 1 was obtained.

<Bridge defect evaluation method>
In the observation of the resist pattern with the dimension of the obtained line pattern and space pattern of 2: 1, using KLA Tencor 2360, the pixel size of the defect inspection apparatus is set to 0.16 μm, and the threshold is set to 20, Measurements were made in random mode to detect development defects extracted from the differences caused by the comparison image and pixel unit overlay. Thereafter, the number of bridge defects (number / cm ² ) per unit area on the wafer was measured by SEMVISION G3 (manufactured by APPLIED MATERIALS).

  Table 7 shows the evaluation results when the number of bridge defects in Example 9 is normalized as 1.

  Further, for comparison, an observation image (FIG. 2B) of the reverse pattern obtained by the pattern formation method of Example 9 and the reverse pattern scan electron obtained by the pattern formation method of Comparative Example 1 were used. The observation image by a microscope (FIG. 2C) is shown.

  From these results, it can be seen that a reverse pattern in which bridge defects are suppressed can be obtained by the pattern forming method of the present invention.

DESCRIPTION OF SYMBOLS 10 ... Substrate 20 ... Processed layer 30 ... 1st film | membrane (Actinic-ray sensitive or radiation sensitive film | membrane)
30a: First pattern (negative pattern)
31a: Space (recessed part)
31b ... Remaining film part (convex part)
40 ... Second film (pattern inversion film)
40a ... second pattern (reversal pattern)

Claims (10)

(A) a step of applying an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) whose polarity is increased by the action of an acid onto a substrate to form a first film;
(B) exposing the first film;
(C) patterning the exposed first film by development to form a first pattern;
(D) applying a resin composition for pattern reversal on the first pattern to form a second film; and
(E) A pattern forming method including a step of patterning a second film by removing a first pattern using a treatment liquid and forming a second pattern in which the shape of the first pattern is reversed. ,
The pattern reversal resin composition contains two or more kinds of resins, and at least two kinds of the resins have different dissolution rates in the treatment liquid.   The pattern forming method according to claim 1, wherein the developing step (c) is a step of forming a negative pattern by developing the first film using a developer containing an organic solvent.   The pattern formation method according to claim 1, wherein the treatment liquid is an alkaline solution.   Among at least two types of resins having different dissolution rates in the treatment liquid, the resin contains at least one alkali-soluble resin as a resin having a higher dissolution rate in the treatment liquid and has a lower dissolution rate in the treatment liquid. The pattern formation method of any one of Claims 1-3 containing at least 1 sort (s) of alkali-insoluble resin as. Of at least two resins having different dissolution rates in the treatment liquid, at least one resin having a higher dissolution rate in the treatment liquid is contained in fluorine atoms, silicon atoms, and side chain portions of the resin. having CH ₃ parts of any one or more structures, the pattern forming method according to any one of claims 1-4.   The pattern formation method of any one of Claims 1-5 including the process of baking at least once between a image development process (c) and a pattern inversion process (e).   Baking process between the development process (c) and the second film forming process (d) and between the second film forming process (d) and the pattern reversal process (e). The pattern formation method of Claim 6 containing this.   The pattern formation method according to claim 1, wherein the pattern reversal resin composition further contains a thermal acid generator.   The manufacturing method of an electronic device containing the pattern formation method of any one of Claims 1-8.   A pattern reversal resin composition used in a pattern forming method for removing a resist pattern with an alkaline solution to obtain a reversal pattern for the resist pattern, the pattern comprising two types of resins having different dissolution rates in the alkaline solution Inversion resin composition.